Shaped porous carbon products

ABSTRACT

Shaped porous carbon products and processes for preparing these products are provided. The shaped porous carbon products can be used, for example, as catalyst supports and adsorbents. Catalyst compositions including these shaped porous carbon products, processes of preparing the catalyst compositions, and various processes of using the shaped porous carbon products and catalyst compositions are also provided.

REFERENCE TO RELATED APPLICATIONS

This application is a division of U.S. non-provisional application Ser.No. 15/441,732, filed Feb. 24, 2017, which is a division of U.S.non-provisional application Ser. No. 14/699,942, filed Apr. 29, 2015 andissued as U.S. Pat. No. 9,682,368, and claims priority to U.S.provisional application Ser. No. 61/985,988 and Ser. No. 61/986,009,both filed Apr. 29, 2014, the entire disclosures of which areincorporated herein by reference.

FIELD OF THE INVENTION

The present invention generally relates to shaped porous carbon productsand processes for preparing these products. The shaped porous carbonproducts can be used, for example, as catalyst supports, chromatographicsupport material, filtration media and adsorbents. The present inventionalso relates to catalyst compositions including these shaped porouscarbon products, processes of preparing the catalyst compositions, andvarious processes of using the shaped porous carbon products and thecatalyst compositions.

BACKGROUND OF THE INVENTION

Carbon is a material that can be deployed as a catalyst support oradsorbent. The most commonly used carbon based supports for chemicalcatalysis are activated carbons exhibiting high specific surface areas(e.g., over 500 m²/g). Preparing activated carbon requires activating acarbonaceous material such as charcoal, wood, coconut shell orpetroleum-sourced carbon black either by a chemical activation, such ascontacting with an acid at high temperatures, or by steam activation.Both methods of activation produce high concentrations of micropores andconsequently higher surface areas. Depending upon the source of thecarbonaceous material, the resultant activated carbons may have a highresidual content of inorganic ash and sulfur, and possibly oxygen ornitrogen-containing functional groups at the surface. Activated carbonsare thought to possess an optimum support structure for catalyticapplications as they enable good dispersion of catalytically activecomponents and effective adsorption and reaction of chemical reagents atthe catalyst surface.

In recent years, there has been a growing interest in using biorenewablematerials as a feedstock to replace or supplement crude oil. See, forexample, Klass, Biomass for Renewable Energy, Fuels, and Chemicals,Academic Press, 1998. This publication and all other cited publicationsare incorporated herein by reference. One of the major challenges forconverting biorenewable resources such as carbohydrates (e.g., glucosederived from starch, cellulose or sucrose) to current commodity andspecialty chemicals is the selective removal of oxygen atoms from thecarbohydrate. Approaches are known for converting carbon-oxygen singlebonds to carbon-hydrogen bonds. See, for example, U.S. Pat. No.8,669,397, which describes a process for the conversion of glucose toadipic acid via the intermediate glucaric acid. One challenging aspectassociated with the catalytic conversions of highly functionalizedbiorenewably-derived molecules and intermediates is reaching the highlevels of catalytic activity, selectivity and stability necessary forcommercial applications. With respect to catalytic activity andselectivity, highly functionalized, biorenewably-derived molecules andintermediates derived from carbohydrates (e.g., glucose and glucaricacid) are non-volatile and must therefore be processed as solutions inthe liquid phase. When compared to gas phase catalytic processes, liquidphase catalytic processes are known to suffer from lower productivitiesbecause liquid to solid (and gas to liquid to solid) diffusion rates areslower than gas to solid diffusion rates.

Another challenging aspect associated with the catalytic conversion ofhighly functionalized biorenewably-derived molecules and intermediatesis the use of chemically aggressive reaction conditions. For example,U.S. Pat. No. 8,669,397 describes catalytic conversion steps performedat elevated temperatures in the presence of polar solvents such as waterand acetic acid. Polar solvents are typically required for thedissolution of non-volatile, highly-functionalized molecules such asglucose and glucaric acid, and elevated temperatures are required forproductive and affordable catalytic conversion steps for commoditychemical applications. Therefore, a significant challenge associatedwith the catalytic conversion of highly functionalizedbiorenewably-derived molecules and intermediates is catalyst stability.Long term catalyst stability is a necessity for commodity chemicalproduction, meaning that the catalyst must be stable, productive, andselective under reaction conditions for long periods.

The challenges associated with the development of industrial shapedcatalysts, especially in the conversion of biorenewably-derivedmolecules and intermediates, are a) high productivity and selectivityconsistent with an economically viable catalyst at industrial scale, b)mechanical and chemical stability of the shaped catalyst support and c)retention of the catalytically active components by the support and theavoidance of leaching of the catalytically active components into apolar solvent reaction medium. There remains a need for industriallyscalable, highly active, selective and stable catalyst supports andcatalyst compositions that can satisfy these challenges.

SUMMARY OF THE INVENTION

Briefly, in various aspects, the present invention is directed to shapedporous carbon products. In accordance with various embodiments, theshaped porous carbon products comprise carbon black and a carbonizedbinder comprising a carbonization product of a water soluble organicbinder, wherein the shaped porous carbon products have a BET specificsurface area from about 20 m²/g to about 500 m²/g, a mean pore diametergreater than about 5 nm, a specific pore volume greater than about 0.1cm³/g, a radial piece crush strength greater than about 4.4 N/mm (1lb/mm), and a carbon black content of at least about 35 wt. %. Inaccordance with other embodiments, the shaped porous carbon productscomprise a carbon agglomerate, wherein the shaped porous carbon productshave a mean diameter of at least about 50 μm, a BET specific surfacearea from about 20 m²/g to about 500 m²/g or from about 25 m²/g to about250 m²/g, a mean pore diameter greater than about 5 nm, a specific porevolume greater than about 0.1 cm³/g, and a radial piece crush strengthgreater than about 4.4 N/mm (1 lb/mm).

In further aspects, the present invention is directed to methods forpreparing shaped porous carbon products. In accordance with variousembodiments, one method of preparing a shaped porous carbon productcomprises mixing water, carbon black, and a water soluble organic binderto produce a carbon black mixture; forming the carbon black mixture toproduce a shaped carbon black composite; and heating the shaped carbonblack composite to carbonize the binder to a water insoluble state toproduce the shaped porous carbon product.

Aspects of the present invention are also directed to various catalystcompositions and methods for preparing the catalyst compositions. Forexample, a catalyst composition according to various embodimentscomprises a shaped porous carbon product as a catalyst support and acatalytically active component or precursor thereof at a surface of thesupport. Another catalyst composition comprises a shaped porous carbonsupport and a catalytically active component or precursor thereofcomprising platinum and gold at a surface of the support. Still anothercatalyst composition comprises a shaped porous carbon support and acatalytically active component or precursor thereof comprising platinumand rhodium at a surface of the support. Methods of preparing a catalystcomposition in accordance with the present invention comprise depositinga catalytically active component or precursor thereof on a shaped porouscarbon product.

In other aspects, the present invention is further directed to variousprocesses of using the shaped porous carbon products and the catalystcompositions. One process in accordance with the present invention isfor the catalytic conversion of a reactant comprising contacting aliquid medium comprising the reactant with a catalyst composition of thepresent invention. Other processes include the selective oxidation of analdose to an aldaric acid and the selective hydrodeoxygenation ofaldaric acid or salt, ester, or lactone thereof to a dicarboxylic acid.Moreover, the present invention is directed to methods of preparing areactor vessel for a liquid phase catalytic reaction. The methodscomprise charging the reactor vessel with a catalyst composition of thepresent invention.

Other objects and features will be in part apparent and in part pointedout hereinafter.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 provides a scanning electron microscopy image of thecross-section of a sample of the catalyst extrudate prepared withMonarch 700 carbon black.

FIG. 2 provides a magnified view of one of catalyst extrudatecross-sections of FIG. 1.

FIG. 3 presents a plot of the cumulative pore volume (%) as a functionof mean pore diameter for a raw Monarch 700 carbon black material.

FIG. 4 presents a plot of the cumulative pore volume (%) as a functionof mean pore diameter for a fresh catalyst extrudate including theMonarch 700 carbon black material.

FIG. 5 presents a plot of the cumulative pore volume (%) as a functionof mean pore diameter for a catalyst extrudate including the Monarch 700carbon black material following 350 hours of use.

FIG. 6 presents a plot of the cumulative pore volume (%) as a functionof mean pore diameter for an extrudate using Monarch 700 carbon blackand a glucose/hydroxyethyl cellulose binder.

FIG. 7 presents a plot of the cumulative pore volume (%) as a functionof mean pore diameter for an extrudate using Sid Richardson SC159 carbonblack and a glucose/hydroxyethyl cellulose binder.

FIG. 8 presents a plot of the cumulative pore volume (%) as a functionof mean pore diameter for a extrudate using Sid Richardson SC 159 carbonblack and a glucose/hydroxyethyl cellulose binder which has been exposedto oxygen at 300° C. for 3 hours.

FIG. 9 presents a plot of the cumulative pore volume (%) as a functionof mean pore diameter for an extrudate using Asbury 5368 carbon blackand a glucose/hydroxyethyl cellulose binder.

FIG. 10 presents a plot of the cumulative pore volume (%) as a functionof mean pore diameter for an activated carbon extrudate of Süd ChemieG32H-N-75.

FIG. 11 presents a plot of the cumulative pore volume (%) as a functionof mean pore diameter for an activated carbon extrudate of DonauSupersorbon K4-35.

FIG. 12 presents the pore size distribution for an extrudate using SidRichardson SC159 carbon black and a glucose/hydroxyethyl cellulosebinder measured by mercury porosimetry.

DETAILED DESCRIPTION

The present invention generally relates to shaped porous carbon productsand processes for preparing these products. The shaped porous carbonproducts can be used, for example, as catalyst supports, chromatographicsupport material, filtration media, adsorbents, and the like. Thepresent invention also relates to catalyst compositions including theseshaped porous carbon products, processes of preparing the catalystcompositions, and various processes of using the shaped porous carbonproducts and catalyst compositions.

The present invention provides shaped porous carbon products thatexhibit high mechanical strength and are resistant to crushing andattrition during use. Further, the shaped porous carbon products possessexcellent chemical stability to reactive solvents such as acids andother polar solvents even at elevated temperatures. The shaped porouscarbon products are highly suited for liquid phase catalytic reactionsbecause they provide for effective mass transfer of compounds havingrelatively large molecular volumes to and away the surface of thesupport.

The present invention also provides processes for preparing the shapedporous carbon products. The shaped porous carbon products can beprepared from inexpensive and readily available materials whichadvantageously improves process economics. Furthermore, the disclosedprocesses are suited for preparation of robust, mechanically strong,shaped porous carbon products through the use of water soluble organicbinders. These processes avoid the use of organic solvents that requirespecial handling and storage.

The present invention further provides catalyst compositions comprisingthe shaped porous carbon products as catalyst supports and processes forpreparing these catalyst compositions. The shaped porous carbon productsexhibit a high degree of retention of the catalytically activecomponent(s) of the catalyst compositions, which beneficially avoids orreduces the amount of catalytically active material leached into aliquid phase reaction medium. Further, the catalyst compositions possessa high degree of stability which is necessary for commodity chemicalproduction.

Further, the present invention provides processes utilizing shapedporous carbon products and catalyst compositions, such as for theconversion of biorenewably-derived molecules and intermediates forcommodity applications (e.g., the selective oxidation of glucose toglucaric acid) or for applications requiring adsorption of compoundshaving relatively large molecular volumes. Surprisingly, it has beenfound that the shaped porous carbon products exhibit a superiormechanical strength (e.g., mechanical piece crush strength and/or radialpiece crush strength), and the use of catalyst compositions comprisingthe shaped porous carbon products of the present invention providesunexpectedly higher productivity, selectivity and/or yield in certainreactions when compared to similar catalysts compositions with differentcatalyst support materials.

Shaped Porous Carbon Products and Methods of Preparation

The shaped porous carbon products of the present invention can beprepared with carbon black. Carbon black materials include varioussubtypes including acetylene black, conductive black, channel black,furnace black, lamp black and thermal black. The primary processes formanufacturing carbon black are the furnace and thermal processes.Generally, carbon black is produced through the deposition of solidcarbon particles formed in the gas phase by combustion or thermalcracking of petroleum products. Carbon black materials are characterizedby particles with diameters in the nanometer range, typically from about5 to about 500 nm. These materials also have much lower surface areas, ahigher concentration of mesopores, and lower ash and sulfur content whencompared to activated carbons. Carbon black materials are deployedcommercially for many applications such as fillers, pigments,reinforcement materials and viscosity modifiers. However, due to theirvery low surface areas, carbon black materials are not typically used assupports for chemical catalysis or adsorbents. Low surface area carbonblack materials can be considered non-optimal as support structures forcatalytic applications because low surfaces areas are considereddetrimental to effective dispersion of catalytically active componentsleading to poor catalytic activity.

As noted, activated carbons are thought to possess an optimum supportstructure for catalytic applications as they enable good dispersion ofcatalytically active components and effective adsorption and reaction ofchemical reagents at the catalyst surface. In contrast, the use ofcarbon black as a catalyst support has been limited. In order to utilizecarbon blacks as supports for chemical catalysis, several groups havereported methods to modify carbon black materials. Reportedmodifications are centered on methods to increase the surface area ofthe carbon black materials. U.S. Pat. No. 6,337,302 describes a processto render a “virtually useless” carbon black into an activated carbonfor commodity applications. U.S. Pat. No. 3,329,626 describes a processto convert carbon black materials with surface areas from 40-150 m²/g bysteam activation into activated carbons with surface areas up to around1200 m²/g.

Notwithstanding these teachings, it has been surprisingly discoveredthat certain carbon black materials exhibiting particular combinationsof characteristics such as surface area, pore volume, and pore diameterare highly effective for use in shaped porous carbon catalyst supportsfor catalytic reactions including liquid and mixed phase reactionmediums. The shaped porous carbon products of the present invention canbe shaped into mechanically strong, chemically stable robust forms thatcan reduce resistance to liquid and gas flows, withstand desired processconditions, and provide for long term, stable catalytic operation. Theseshaped porous carbon products provide high productivity and highselectivity during long term continuous flow operation under demandingreaction conditions including liquid phase reactions in which thecatalyst composition is exposed to reactive solvents such as acids andwater at elevated temperatures.

Carbon black may constitute a large portion of the shaped porous carbonproduct of the present invention. As such, the carbon black content ofthe shaped porous carbon product is at least about 35 wt. % or more suchas at least about 40 wt. %, at least about 45 wt. %, at least about 50wt. %, at least about 55 wt. %, at least about 60 wt. %, at least about65 wt. %, or at least about 70 wt. %. In various embodiments, the carbonblack content of the shaped porous carbon product is from about 35 wt. %to about 80 wt. %, from about 35 wt. % to about 75 wt. %, from about 40wt. % to about 80 wt. %, or from about 40 wt. % to about 75 wt. %.

Typically, the carbon black materials used to prepare a shaped porouscarbon product of the present invention have a BET specific surface areain the range of from about 20 m²/g to about 500 m²/g. In variousembodiments, the BET specific surface area of the carbon black is in therange of from about 20 m²/g to about 350 m²/g, from about 20 m²/g toabout 250 m²/g, from about 20 m²/g to about 225 m²/g, from about 20 m²/gto about 200 m²/g, from about 20 m²/g to about 175 m²/g, from about 20m²/g to about 150 m²/g, from about 20 m²/g to about 125 m²/g, or fromabout 20 m²/g to about 100 m²/g, from about 25 m²/g to about 500 m²/g,from about 25 m²/g to about 350 m²/g, from about 25 m²/g to about 250m²/g, from about 25 m²/g to about 225 m²/g, from about 25 m²/g to about200 m²/g, from about 25 m²/g to about 175 m²/g, from about 25 m²/g toabout 150 m²/g, from about 25 m²/g to about 125 m²/g, from about 25 m²/gto about 100 m²/g, from about 30 m²/g to about 500 m²/g, from about 30m²/g to about 350 m²/g, from about 30 m²/g to about 250 m²/g, from about30 m²/g to about 225 m²/g, from about 30 m²/g to about 200 m²/g, fromabout 30 m²/g to about 175 m²/g, from about 30 m²/g to about 150 m²/g,from about 30 m²/g to about 125 m²/g, or from about 30 m²/g to about 100m²/g. The specific surface area of carbon black materials is determinedfrom nitrogen adsorption data using the Brunauer, Emmett and Teller(BET) Theory. See J. Am. Chem. Soc. 1938, 60, 309-331 and ASTM TestMethods ASTM 3663, D6556, or D4567 which are Standard Test Methods forTotal and External Surface Area Measurements by Nitrogen Adsorption andare incorporated herein by reference.

The carbon black materials generally have a mean pore diameter greaterthan about 5 nm, greater than about 10 nm, greater than about 12 nm, orgreater than about 14 nm. In some embodiments, the mean pore diameter ofthe carbon black materials used to prepare the shaped porous carbonproduct is in the range of from about 5 nm to about 100 nm, from about 5nm to about 70 nm greater, from 5 nm to about 50 nm, from about 5 nm toabout 25 nm, from about 10 nm to about 100 nm, from about 10 nm to about70 nm greater, from 10 nm to about 50 nm, or from about 10 nm to about25 nm. Such pore diameters enable effective transport of reactantmolecules possessing large molecular volumes (such asbiorenewably-derived molecules with 6-carbon atom frameworks) into andout of the pore structure of the catalytically active surface, therebyenabling enhanced activity.

The carbon black materials used to prepare the shaped porous carbonproducts of the present invention also generally have specific porevolumes greater than about 0.1 cm³/g, greater than about 0.2 cm³/g, orgreater than about 0.3 cm³/g. The specific pore volume of the carbonblack materials can range from about 0.1 cm³/g to about 1 cm³/g, fromabout 0.1 cm³/g to about 0.9 cm³/g, from about 0.1 cm³/g to about 0.8cm³/g, from about 0.1 cm³/g to about 0.7 cm³/g, from about 0.1 cm³/g toabout 0.6 cm³/g, from about 0.1 cm³/g to about 0.5 cm³/g, from about 0.2cm³/g to about 1 cm³/g, from about 0.2 cm³/g to about 0.9 cm³/g, fromabout 0.2 cm³/g to about 0.8 cm³/g, from about 0.2 cm³/g to about 0.7cm³/g, from about 0.2 cm³/g to about 0.6 cm³/g, from about 0.2 cm³/g toabout 0.5 cm³/g, from about 0.3 cm³/g to about 1 cm³/g, from about 0.3cm³/g to about 0.9 cm³/g, from about 0.3 cm³/g to about 0.8 cm³/g, fromabout 0.3 cm³/g to about 0.7 cm³/g, from about 0.3 cm³/g to about 0.6cm³/g, or from about 0.3 cm³/g to about 0.5 cm³/g. Carbon blackmaterials with these specific pore volumes provide a volume sufficientto provide uniform wetting and good dispersion of the catalyticallyactive components while enabling sufficient contact between the reactantmolecules and the catalytically active surface. Mean pore diameters andpore volumes are determined in accordance with the procedures describedin E. P. Barrett, L. G. Joyner, P. P. Halenda, J. Am. Chem. Soc. 1951,73, 373-380 (BJH method), and ASTM D4222-03(2008) Standard Test Methodfor Determination of Nitrogen Adsorption and Desorption Isotherms ofCatalysts and Catalyst Carriers by Static Volumetric Measurements, whichare incorporated herein by reference.

Certain carbon black materials are known to be electrically conductive.Accordingly, in various embodiments, the shaped porous carbon productcomprises conductive carbon black and in some embodiments, the shapedporous carbon product is electrically conductive. In other embodiments,the shaped porous carbon product comprises nonconductive carbon black.In further embodiments, the shaped porous carbon product comprisesnonconductive carbon black wherein the shaped porous carbon product doesnot exhibit a conductivity that is suitable for a conductive electrode.In certain embodiments, the shaped porous carbon product comprisesnonconductive carbon black and less than about 50%, less than about 40%,less than about 30%, less than about 20%, less than about 10%, less thanabout 5%, or less than about 1% conductive carbon black based on thetotal weight of the carbon black in the shaped porous carbon productand/or the total weight of the carbon black used to prepare the shapedporous carbon product. In some embodiments, the shaped porous carbonproduct comprises carbon black consisting of or consisting essentiallyof nonconductive carbon black. In some embodiments, the carbon blackcomprises a silica-bound or alumina-bound carbon black. In certainembodiments, the shaped porous carbon product can further includegraphite and/or a metal oxide (e.g., alumina, silica, titania, and thelike).

The shaped porous carbon product comprising carbon black may be preparedby various methods such as dry powder pressing, drip casting, injectionmolding, 3D-printing, extrusion and other pelletizing and granulatingmethods. For example, dry powder pressing involves compressing carbonblack particles in a press such as a hot or cold isostatic press or acalandering press. Other pelletizing and granulating methods includetumbling carbon black particles and contacting the particles with aspray containing a binder.

Various methods of preparing the shaped porous carbon product comprisemixing water, carbon black, and a binder to form a carbon black mixture;forming the carbon black mixture to produce a shaped carbon blackcomposite; heating the shaped carbon black composite to carbonize thebinder to a water insoluble state and to produce a shaped porous carbonproduct. In various methods of preparing the shaped porous carbonproducts, a binder solution can be prepared by mixing water and thebinder prior to mixing with carbon black. Typically, the binder solutionand carbon black mixture are relatively concentrated in binder. Forexample, the water content of the carbon black mixture is typically nomore than about 80% by weight, no more than about 55% by weight, no morethan about 40% by weight, or no more than about 25% by weight. Invarious embodiments, the water content of the carbon black mixture canbe from about 5 wt. % to about 70 wt. %, from about 5 wt. % to about 55wt. %, from about 5 wt. % to about 40 wt. %, or from about 5 wt. % toabout 25 wt. %. The viscosity of the binder solution can vary, forexample, according to the binder content and can be readily adjusted tosuit a particular shaping process by varying the relative quantities ofsolid and liquid components. For example, the viscosity of the aqueoussolution can be varied by adjusting the amount of binder and type ofbinder utilized. Also in various methods, the water and binder can bemixed and heated to form the binder solution. In some instances, heatingcan enhance the amount of binder that can be incorporated into thebinder solution and/or carbon black mixture (e.g., by increasing thesolubility of the binder). For example, the water and binder can beheated to a temperature of at least about 50° C., at least about 60° C.,or at least about 70° C. In various embodiments, the water and bindercan be heated to a temperature of from about 50° C. to about 95° C.,from about 50° C. to about 90° C., or from about 60° C. to about 85° C.

After mixing and heating to form the binder solution, the bindersolution can be cooled as needed prior to mixing with carbon black orprior to forming the shaped carbon black composite.

One method of preparing the shaped porous carbon product of the presentinvention comprises mixing carbon black particles with a solutioncomprising a binder to produce a slurry; forming the slurry (e.g., byextrusion) to produce a shaped carbon black composite and heating orpyrolyzing the shaped carbon black composite to carbonize the binder toproduce the shaped porous carbon product.

In various methods of preparing the shaped porous carbon product of thepresent invention as described herein, a binder solution or binder andwater are thoroughly mixed and blended with the carbon black to preparea carbon black mixture (e.g., a slurry or a paste). The weight ratio ofbinder to carbon black in the carbon black mixture is typically at leastabout 1:4, at least about 1:3, at least about 1:2, at least about 1:1,or at least 1.5:1. The weight ratio of binder to carbon black in thecarbon black mixture can also be from about 1:4 to about 3:1, from about1:4 to about 1:1, from about 1:3 to about 2:1, from about 1:3 to about1:1, or about 1:1. Typically, the carbon black content of the carbonblack mixture is at least about 35 wt. % or more such as at least about40 wt. %, at least about 45 wt. %, as at least about 50 wt. %, as atleast about 55 wt. %, at least about 60 wt. %, at least about 65 wt. %,or at least about 70 wt. % on a dry weight basis. In variousembodiments, the carbon black content of the carbon black mixture isfrom about 35 wt. % to about 80 wt. %, from about 35 wt. % to about 75wt. %, from about 40 wt. % to about 80 wt. %, or from about 40 wt. % toabout 75 wt. % on a dry weight basis. Also, the binder content of thecarbon black mixture is typically at least about 10 wt. %, at leastabout 20 wt. %, at least about 25 wt. %, at least about 30 wt. %, atleast about 35 wt. %, at least about 40 wt. %, or at least 45 wt. % on adry weight basis. In various methods for preparing the shaped porouscarbon product of the present invention as described herein, the bindercontent of the carbon black mixture is from about 10 wt. % to about 50wt. %, from about 10 wt. % to about 45 wt. %, from about 15 wt. % toabout 50 wt. %, from about 20 wt. % to about 50 wt. %, or from about 20wt. % to about 45 wt. % on a dry weight basis.

Various methods of preparing the shaped porous carbon products canfurther comprise pressing or kneading the carbon black mixture. Pressingor kneading the carbon black mixture compacts the mixture and can reducethe water content of the mixture. Pressing or kneading of the water,carbon black and binder (carbon black mixture) can be conductedsimultaneously with the mixing of the water, carbon black and binder.For example, one method of mixing the water, carbon black, and binderand simultaneously pressing the resulting carbon black mixture can beconducted using a mixer muller.

After mixing of the carbon black and binder, the resulting carbon blackmixture is formed into a shaped carbon black composite structure of thedesired shape and dimensions by a forming technique such as extrusion,pelletizing, pilling, tableting, cold or hot isostatic pressing,calandering, injection molding, 3D printing, drip casting, or othermethods known to produce shaped structures. Forming methods such as coldor hot isostatic pressing and 3D printing may or may not require abinder.

In general, the shaped porous carbon product can be shaped and sized foruse in known industrial reactor formats such as batch slurry, continuousslurry-based stirred tank reactors, fixed beds, ebulated beds and otherknown industrial reactor formats. The shaped porous carbon product maybe formed into various shapes including spheres, beads, cylinders,pellets, multi-lobed shapes, rings, stars, ripped cylinders, triholes,alphas, wheels, etc. Also, the shaped porous carbon product may beformed into amorphous, non-geometric, and random shapes as well asunsymmetrical shapes like hiflow rings and cones and alpha-rings. Themean diameter of the shaped porous carbon product is typically at leastabout 50 μm (0.05 mm), at least about 500 μm (0.5 mm), at least about1,000 μm (1 mm), at least about 10,000 μm (10 mm) or larger toaccommodate process requirements.

For extrusion forming, a pressure of at least about 100 kPa (1 bar) orbetween about 100 kPa (1 bar) to about 10,000 kPa (100 bar), between 500kPa (5 bar) and 5,000 kPa (50 bar), or between 1,000 kPa (10 bar) and3,000 kPa (30 bar) is typically applied to the carbon black mixture.

In drip casting methods, the carbon black mixture comprising carbonblack particles and the binder are dispensed as droplets into a castingbath to form the shaped carbon black composite, which is then separatedfrom the casting bath. Carbon black mixture droplets of a tailoreddiameter may be dispensed through a sized nozzle and dropped into a bathto produce solidified, spherically-shaped carbon black composite ofvarious diameters. In various embodiments of this method, the bindercomprises an alginate (or alginate in combination with anothercarbohydrate binder as described herein) which can be dispensed into abath containing a reagent to cause solidification such as an ionic salt(e.g., calcium salt) as described in U.S. Pat. No. 5,472,648, the entirecontents of which are incorporated herein by reference. The droplets aresubsequently allowed to remain substantially free in the ionic solutionuntil the required degree of solidification and consolidation has beenattained. Alternatively, the drip casting bath utilized may be, forexample, an oil bath, or a bath to cause freeze drying. When an oil bathis used, the temperature of the oil is sufficiently high that the binderis thermally set (e.g., causes the binder to convert to athree-dimensional gel). When a freeze drying bath is used, the resultantbeads are typically dried by vacuum treatment. The shaped carbon blackcomposites resulting from such dip casting methods are subsequentlypyrolyzed.

As described in further detail below, other components can be added tothe carbon black mixture to assist with the shaping process (e.g.,lubricants, compatibilizers, etc.) or to provide other benefits. Invarious embodiments, the carbon black mixture further comprises aforming adjuvant. For example, the forming adjuvant can comprise alubricant. Suitable forming adjuvants include, for instance, lignin orlignin derivatives.

Further, porogens may be mixed with the carbon black and binder tomodify and attain the desired pore characteristics in the shaped porouscarbon product. Other methods of modifying the porosity of the shapedporous carbon product include mixing two or more different carbon blackstarting materials (e.g., carbon blacks having different shape and/orsize that pack irregularly resulting in multimodal pore sizedistributions, or carbon blacks from different sources/suppliers, ormixing carbon black powders carbon. Other methods of modifying theporosity of the shaped porous carbon product include multiple thermalprocessing and/or multiple compounding (e.g., pyrolysis of a shapedcarbon black composite of carbon powder and binder, then mixing withfresh carbon black powder and binder and pyrolyzing the resultantcomposite again).

In various methods of preparing the shaped porous carbon product, afterprocessing the carbon black mixture (e.g., a slurry or a paste) into theshaped carbon black composite, the composite may be dried to dehydratethe composite. Drying may be achieved by heating the composite atatmospheric pressure and temperatures typically of from about roomtemperature (e.g., about 20° C.) to about 150° C., from about 40° C. toabout 120° C., or from about 60° C. to about 120° C. Other methods ofdrying may be utilized including vacuum drying, freeze drying, anddesiccation. When using certain preparation methods for forming (e.g.,tableting, pressing), no drying step may be required.

In various methods of preparing the shaped porous carbon product, theshaped carbon black composite (e.g., resulting from extrusion,pelletizing, pilling, tableting, cold or hot isostatic pressing,calandering, injection molding, 3D printing, drip casting, and otherforming methods) is heat treated in an inert (e.g., an inert nitrogenatmosphere), oxidative, or reductive atmosphere to carbonize at least aportion of the binder to a water insoluble state and produce a shapedporous carbon product. The heat treatment is typically conducted at atemperature of from about 250° C. to about 1,000° C., from about 300° C.to about 900° C., from about 300° C. to about 850° C., from about 300°C. to about 800° C., from about 350° C. to about 850° C., from about350° C. to about 800° C., from about 350° C. to about 700° C., fromabout 400° C. to about 850° C. or from about 400° C. to about 800° C. Insome instances and depending upon the binder employed, it has beendetermined that lower carbonization temperatures can lead to slowleaching of the remnants of the binder from the shaped porous carbonproduct which reduces mechanical strength over extended periods of usein catalytic reactions. Generally, to ensure longer term stability, theheat treatment is conducted at higher carbonization temperatures withinthe ranges specified above. In some instances, the resultant shapedporous carbon product may be washed after the heat treatment to removeimpurities.

In accordance with various preparation methods, shaped porous carbonproducts of the present invention comprise a binder or carbonizationproduct thereof in addition to carbon black. Various references,including U.S. Pat. No. 3,978,000, describe the use of acetone solubleorganic polymers and thermosetting resin as binders for shaped carbonsupports. However, the use of flammable organic solvents and expensivethermosetting resins is not desirable or economical for manufacturinglarge quantities of shaped porous carbon product.

Mechanically-strong, shaped porous carbon products of the invention canbe prepared by the use of an effective binder. The use of an effectivebinder provides a robust shaped porous carbon product capable ofwithstanding the prevailing conditions within continuous liquid phaseflow environments such as in conversions of biorenewably-derivedmolecules or intermediates in which the liquid phase may contain wateror acidic media. In such instances the shaped porous carbon product ismechanically and chemically stable to enable long-term operation withoutsignificant loss in catalyst performance. Moreover, the use of aneffective binder provides a robust shaped porous carbon product capableof withstanding elevated temperatures.

Applicants have found that readily available water soluble organiccompounds are suitable binders for the preparation of mechanicallystrong shaped porous carbon products. As used in herein, a binder isdeemed water soluble if the solubility at 50° C. is at least about 1 wt.%, preferably at least about 2 wt. %. Aqueous solutions of organicbinders are highly amenable to commercial manufacturing methods. Organicbinders that dissolve in aqueous solutions enable good mixing anddispersion when contacted with the carbon black materials. These bindersalso avoid safety and processing issues associated with large-scale useof organic solvents which may be flammable and require special storageand handling. Also, these binders are relatively inexpensive whencompared to costly polymer-based binders. As such, in variousembodiments, the carbon black mixtures do not contain water immisciblesolvents.

In various embodiments, the water soluble organic binder comprises acarbohydrate or derivative thereof, which may be a monomeric oroligomeric or polymeric carbohydrate (also known as saccharides,oligosaccharide and polysaccharides). Derivatives of carbohydrates (inmonomeric or oligomeric polymeric forms) are also included wherein afunctional group or groups bound to the carbohydrate may be exchanged orderivatized. Such derivatives may be acidic or charged carbohydratessuch as alginic acid or alginate salts, or pectin, or aldonic acids,aldaric acids, uronic acids, xylonic or xylaric acids (or oligomers, orpolymers or salts thereof). Other derivatives include sugar alcohols andpolymeric forms thereof (e.g., sorbitol, mannitol, xylitol or polyolsderived from carbohydrates). The carbohydrate binder may be used in theform of syrups such as molasses or corn syrups or soluble starches orsoluble gum or modified versions thereof.

In various embodiments, the water soluble organic binder comprises asaccharide selected from the group consisting of a monosaccharide, adisaccharide, an oligosaccharide, a derivative thereof, and anycombination thereof. In these and other embodiments, the water solubleorganic binder comprises: (i) a saccharide selected from the groupconsisting of a monosaccharide, a disaccharide, an oligosaccharide, aderivative thereof, and any combination thereof and (ii) a polymericcarbohydrate, a derivative of a polymeric carbohydrate, or anon-carbohydrate synthetic polymer, or any combination thereof. Theweight ratio of (i) the saccharide to (ii) the polymeric carbohydrate,derivative of the polymeric carbohydrate, or the non-carbohydratesynthetic polymer, or combination thereof can be from about 5:1 to about50:1, from about 10:1 to about 25:1, or from about 10:1 to about 20:1.

In various embodiments, the water soluble organic binder comprises amonosaccharide. For example, the monosaccharide can be selected from thegroup consisting of glucose, fructose, hydrates thereof, syrups thereof(e.g., corn syrups, molasses, and the like) and combinations thereof. Infurther embodiments, the water soluble organic binder comprises adisaccharide. Disaccharides include for example, maltose, sucrose, syrupthereof, and combinations thereof.

As noted, the binder can comprises a polymeric carbohydrate, derivativeof a polymeric carbohydrate, or a non-carbohydrate synthetic polymer, orany combination thereof. In various embodiments, the binder comprises apolymeric carbohydrate, derivative of a polymeric carbohydrate, or anycombination thereof. The polymeric carbohydrate or derivative of thepolymeric carbohydrate can comprise a cellulosic compound. Cellulosiccompounds include, for example, methylcellulose, ethylcellulose,ethylmethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose,methylhydroxyethylcellulose, ethylhydroxyethylcellulose,hydroxypropylmethylcellulose, carboxymethylcellulose, and mixturesthereof.

Further, the polymeric carbohydrate or derivative of the polymericcarbohydrate derivative can be selected from the group consisting ofalginic acid, pectin, aldonic acids, aldaric acids, uronic acids, sugaralcohols, and salts, oligomers, and polymers thereof. The polymericcarbohydrate or derivative of the polymeric carbohydrate can alsocomprise a starch or a soluble gum.

In various embodiments, the water soluble organic binder comprises acellulosic compound. In another embodiment, the binder comprises anacidic polysaccharide such as alginic acid, pectin or a salt thereof. Inother embodiments, the binder comprises a soluble cellulose such as analkyl cellulose (e.g., hydroxyethylcellulose, hydroxypropylcellulose,hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, andcarboxymethylcellulose).

In various embodiments, the binder comprises a non-carbohydratesynthetic polymer. Water soluble polymers or copolymers may be used asbinders. For example, polyacrylic acid, polyvinyl alcohols,polyvinylpyrrolidones, polyvinyl acetates, polyacrylates, polyethers(such as, for example, polyethyelene glycol and the like) and copolymers(which can be block copolymers comprising a water insoluble blockmonomers and water soluble block monomers) derived therefrom, and blendsthereof. In some instances, the water soluble copolymer may be a blockcopolymer comprising a water soluble polymer block and a second polymerblock which may be hydrophobic and amenable to carbonization (e.g.,polystyrene). In another embodiment, polymer dispersions in water areused as binders, i.e., non-water soluble polymers dispersed in water(with the aid of surfactants) such as commercial polyvinyl alcohol,polyacrylonitrile, polyacrylonitrile-butadiene-styrene, phenolic polymeror lignin polymer dispersions. Also copolymers consisting of awater-soluble branch (e.g., polyacrylic acid) and a hydrophobic branch(e.g., polymaleic anhydride, polystyrene) enabling water solubility ofthe copolymer and enabling carbonization of the hydrophobic branchwithout depolymerisation upon pyrolysis. Carbohydrates or derivativesthereof, water soluble polymers and polymer dispersions in water may beused together in various combinations.

As described above, water soluble organic binders that may be used incombination with the saccharide binders include water soluble cellulosesand starches (e.g., hydroxyethylcellulose, hydroxypropylcellulose,hydroxyethylmethylcellulose, hydroxylpropylmethylcellulose,carboxymethylcellulose), water soluble alcohols (e.g., sorbitol,xylitol, polyvinylalcohols), water soluble acetals (e.g.,polyvinylbutyral), water soluble acids (e.g., stearic acid, citric acid,alginic acid, aldonic acids, aldaric acids, uronic acids, xylonic orxylaric acids (or oligomers, or polymers or salts or esters thereof)polyvinyl acrylic acids (or salts or esters thereof). In someembodiments, the combination of water soluble organic binders comprisesa cellulosic compound and a monosaccharide. In certain embodiments, thecellulosic compound comprises hydroxyethylcellulose, or methylcelluloseand the monosaccharide comprises a glucose, fructose or hydrate thereof(e.g., glucose). In particular, one combination comprises glucose andhydroxyethylcellulose, which provides shaped porous carbon products withenhanced mechanical strength, particularly when processed at highcarbonization temperatures. In other embodiments the combination ofwater soluble organic binders comprises a monosaccharide and awater-soluble alcohol such as sorbitol, mannitol, xylitol or a polyvinylalcohol. In other embodiments, the combination of water soluble organicbinders comprises a monosaccharide, and a water-soluble acid such asstearic acid, pectin, alginic acid or polyacrylic acid (or saltsthereof). In further embodiments, the combination of water solubleorganic binders comprises a monosaccharide and a water-soluble estersuch as a polyacrylate or polyacetate. In still other embodiments, thecombination of water soluble organic binders comprises a monosaccharideand a water-soluble acetal such as a polyacetal (e.g.,polyvinylbutyral).

Other water soluble compounds may be used in combination with acarbohydrate or polymeric binder. Combining a carbohydrate or otherbinder with selected other water soluble organic compounds can provideadvantages in the preparation of and in the properties of the resultantshaped porous carbon product. For example, water soluble organiccompounds such as stearic acid or stearates such as Zr or NH₄ stearatecan provide lubrication during the forming process. Wetting agents maybe added (e.g., GLYDOL series available commercially from Zschimmer andSchwarz).

Porogens may also be added in combination with the binder (or binders).Porogens are typically added to occupy a specific molecular volumewithin the formulation such that after the shaping and thermalprocessing the porogen will be pyrolyzed leaving pores of a certainvolume and diameter within the shaped product. The presence of suchpores can be beneficial to performance. For example, when used as acatalyst support the presence of such pores can lead to more efficientdiffusion (of reactants and products) to and from the catalyticallyactive surfaces. More efficient access and egress for the reactants andproducts can lead to improvements in catalyst productivity andselectivity. Porogens are typically oligomeric (e.g., dimer, trimers ofhigher order oligomers) or polymeric in nature. Water soluble organiccompounds such as water soluble linear and branched polymers andcross-linked polymers are suitable for use as porogens. Polyacrylates(such as weakly cross-linked polyacrylates known as superabsorbers),polyvinyl alcohols, polyvinylacetates, polyesters, polyethers, orcopolymers (which may be block copolymers) thereof may be used asporogens. In some instances, the water soluble copolymer may be a blockcopolymer comprising a water soluble polymer block and a second polymerblock which may be hydrophobic and amenable to carbonization (e.g.,polystyrene). In another embodiment, polymer dispersions in water areused as binders, i.e., non-water soluble polymers dispersed in water(with the aid of surfactants) such as commercial polyvinyl alcohol,polyacrylonitrile, polyacrylonitrile-butadiene-styrene, phenolic polymerdispersions. Also copolymers consisting of a water-soluble branch (e.g.,polyacrylic acid) and a hydrophobic branch (e.g., polymaleic anhydride,polystyrene) enabling water solubility of the copolymer and enablingcarbonization of the hydrophobic branch without depolymerisation uponpyrolysis. Carbohydrates or derivatives thereof, (disaccharides,oligosaccharides, polysaccharides such as sucrose, maltose, trihalose,starch, cellubiose, celluloses), water soluble polymers and polymerdispersions in water may be used together in any combination as aporogen to attain a shaped porous carbon black product having thedesired pore size and volume characteristics described herein.

Porogens can also be added as gels (e.g., pre-gelated superabsorber) orwater insoluble incompressible solids (e.g., polystyrene microbeads,lignins, phenolic polymers) or expandable porogens such as EXPANSELmicrospheres available from Akzo Nobel Pulp and Performance (Sundsvall,Sweden). The molecular weight of the oligomer or polymer can be alsochosen to design a desired pore sizes and volume characteristics of theshaped carbon product of the invention. For example the desired shapedcarbon product may have a monomodal, bimodal or multimodal pore sizedistribution as a consequence of addition of a porogen. Forillustration, a bimodal or multimodal pore size distribution may consistof a high percentage of pores between 10 and 100 nm and additionally thepresence of pores >100 nm. Such a pore structure may provide performanceadvantages. For example, the presence of a such a pore size distributioncan lead to more efficient diffusion (of reactants and products) throughthe larger pore (transport pores) to and from catalytically activesurfaces which reside in the pores sized between 10 and 100 nm. Moreefficient access and egress for the reactants and products can lead toimprovements in catalyst productivity, selectivity, and/or yield.

Following heat treatment of the shaped carbon black composite, theresulting shaped porous carbon product comprises carbon black andcarbonized binder. More generally, the shaped porous carbon product cancomprise a carbon agglomerate. Without being bound by any particulartheory, it is believed that the carbon agglomerate comprises carbonaggregates or particles that are physically bound or entangled at leastin part by the carbonized binder. Moreover, and without being bound byany particular theory, the resulting agglomerate may include chemicalbonding of the carbonized binder with the carbon aggregates orparticles.

The carbonized binder comprises a carbonization product of a watersoluble organic binder as described herein. Carbonizing the binderduring preparation of the shaped porous carbon product may reduce theweight of the shaped carbon black composite from which it is formed.Accordingly, in various embodiments, the carbonized binder content ofthe shaped porous carbon product is from about 10 wt. % to about 50 wt.%, from about 20 wt. % to about 50 wt. %, from about 25 wt. % to about40 wt. %, or from about 25 wt. % to about 35 wt. % (e.g., 30 wt. %).

The specific surface area (BET surface area), mean pore diameter, andspecific pore volume of the shaped porous carbon products are generallycomparable to that exhibited by the carbon black material used toprepare the products. However, the preparation process can lead to areduction or an increase in these characteristics of the products ascompared to the carbon black material (e.g., about a 10-50% or 10-30%decrease or increase). In various embodiments, the shaped porous carbonproduct has a specific surface area from about 20 m²/g to about 500m²/g, from about 20 m²/g to about 350 m²/g, from about 20 m²/g to about250 m²/g, from about 20 m²/g to about 225 m²/g, from about 20 m²/g toabout 200 m²/g, from about 20 m²/g to about 175 m²/g, from about 20 m²/gto about 150 m²/g, from about 20 m²/g to about 125 m²/g, or from about20 m²/g to about 100 m²/g, from about 25 m²/g to about 500 m²/g, fromabout 25 m²/g to about 350 m²/g, from about 25 m²/g to about 250 m²/g,from about 25 m²/g to about 225 m²/g, from about 25 m²/g to about 200m²/g, from about 25 m²/g to about 175 m²/g, from about 25 m²/g to about150 m²/g, from about 25 m²/g to about 125 m²/g, from about 25 m²/g toabout 100 m²/g, from about 30 m²/g to about 500 m²/g, from about 30 m²/gto about 350 m²/g, from about 30 m²/g to about 250 m²/g, from about 30m²/g to about 225 m²/g, from about 30 m²/g to about 200 m²/g, from about30 m²/g to about 175 m²/g, from about 30 m²/g to about 150 m²/g, fromabout 30 m²/g to about 125 m²/g, or from about 30 m²/g to about 100m²/g. The specific surface area of the shaped porous carbon product isdetermined from nitrogen adsorption data using the Brunauer, Emmett andTeller. See the methods described in J. Am. Chem. Soc. 1938, 60, 309-331and ASTM Test Methods D3663, D6556 or D4567, which are Standard TestMethods for Surface Area Measurements by Nitrogen Adsorption.

The shaped porous carbon products typically have a mean pore diametergreater than about 5 nm, greater than about 10 nm, greater than about 12nm, or greater than about 14 nm. In some embodiments, the mean porediameter of the shaped porous carbon product is from about 5 nm to about100 nm, from about 5 nm to about 70 nm, from 5 nm to about 50 nm, fromabout 5 nm to about 25 nm, from about 10 nm to about 100 nm, from about10 nm to about 70 nm, from 10 nm to about 50 nm, or from about 10 nm toabout 25 nm. Also, the shaped porous carbon products of the presentinvention have specific pore volumes of the pores having a diameter of1.7 nm to 100 nm as measured by the BJH method that is generally greaterthan about 0.1 cm³/g, greater than about 0.2 cm³/g, or greater thanabout 0.3 cm³/g. In various embodiments, the shaped porous carbonproducts have a specific pore volume of the pores having a diameter of1.7 nm to 100 nm as measured by the BJH method that is from about 0.1cm³/g to about 1.5 cm³/g, from about 0.1 cm³/g to about 0.9 cm³/g, fromabout 0.1 cm³/g to about 0.8 cm³/g, from about 0.1 cm³/g to about 0.7cm³/g, from about 0.1 cm³/g to about 0.6 cm³/g, from about 0.1 cm³/g toabout 0.5 cm³/g, from about 0.2 cm³/g to about 1 cm³/g, from about 0.2cm³/g to about 0.9 cm³/g, from about 0.2 cm³/g to about 0.8 cm³/g, fromabout 0.2 cm³/g to about 0.7 cm³/g, from about 0.2 cm³/g to about 0.6cm³/g, from about 0.2 cm³/g to about 0.5 cm³/g, from about 0.3 cm³/g toabout 1 cm³/g, from about 0.3 cm³/g to about 0.9 cm³/g, from about 0.3cm³/g to about 0.8 cm³/g, from about 0.3 cm³/g to about 0.7 cm³/g, fromabout 0.3 cm³/g to about 0.6 cm³/g, or from about 0.3 cm³/g to about 0.5cm³/g. Mean pore diameters and specific pore volumes are determined inaccordance with the procedures described in E. P. Barrett, L. G. Joyner,P. P. Halenda, J. Am. Chem. Soc. 1951, 73, 373-380 (BJH method), andASTM D4222-03(2008) Standard Test Method for Determination of NitrogenAdsorption and Desorption Isotherms of Catalysts and Catalyst Carriersby Static Volumetric Measurements, which are incorporated herein byreference.

It has been observed that the magnitude of the specific surface area isgenerally proportional to the concentration of micropores in the shapedporous carbon product structure. In particular, the shaped porous carbonproducts generally possess a low concentration of pores having a meandiameter less than 1.7 nm. Typically, pores having a mean diameter lessthan 1.7 nm constitute no more than about 10%, no more than about 5%, nomore than about 4%, no more than about 3%, or no more than about 2.5% ofthe pore volume of the shaped porous carbon product. Similarly, invarious embodiments, the pore size distribution of the shaped porouscarbon products is such that peaks below about 10 nm or about 5 nm arenot observed. For example, the shaped porous carbon products can have apore size distribution such that the peak of the distribution is at adiameter greater than about 5 nm, greater than about 7.5 nm, greaterthan about 10 nm, greater than about 12.5 nm, greater than about 15 nm,or greater than about 20 nm. Also, the shaped porous carbon product canhave a pore size distribution such that the peak of the distribution isat a diameter less than about 100 nm, less than about 90 nm, less thanabout 80 nm, or less than about 70 nm.

Moreover, the shaped porous carbon product advantageously exhibits ahigh concentration of mesopores between about 10 nm to about 100 nm orbetween about 10 nm to about 50 nm. Accordingly, in various embodiments,at least about 50%, at least about 60%, at least about 70%, at leastabout 80%, or at least about 90% of the pore volume of the shaped porouscarbon product, as measured by the BJH method on the basis of poreshaving a diameter from 1.7 nm to 100 nm, is attributable to pores havinga mean pore diameter of from about 10 nm to about 100 nm. For example,from about 50% to about 95%, from about 50% to about 90%, from about 50%to about 80%, from about 60% to about 95%, from about 60% to about 90%,from about 60% to about 80%, from about 70% to about 95%, from about 70%to about 90%, from about 70% to about 80%, from about 80% to about 95%,or from about 80% to about 90% of the pore volume of the shaped porouscarbon product, as measured by the BJH method on the basis of poreshaving a diameter from 1.7 nm to 100 nm, is attributable to pores havinga mean pore diameter of from about 10 nm to about 100 nm. Also, invarious embodiments, at least about 35%, at least about 40%, at leastabout 45%, or at least about 50% of the pore volume of the shaped porouscarbon product, as measured by the BJH method on the basis of poreshaving a diameter from 1.7 nm to 100 nm, is attributable to pores havinga mean pore diameter of from about 10 nm to about 50 nm. For example,from about 35% to about 80%, from about 35% to about 75%, from about 35%to about 65%, from about 40% to about 80%, from about 40% to about 75%,or from about 40% to about 70% of the pore volume of the shaped porouscarbon product, as measured by the BJH method on the basis of poreshaving a diameter from 1.7 nm to 100 nm, is attributable to pores havinga mean pore diameter of from about 10 nm to about 50 nm.

Typically, the shaped porous carbon product exhibits a relatively lowconcentration of pores less than 10 nm, less than 5 nm, or less than 3nm. For example, no more than about 10%, no more than about 5%, or nomore than about 1% of the pore volume of the shaped porous carbonproduct, as measured by the BJH method on the basis of pores having adiameter from 1.7 nm to 100 nm, is attributable to pores having a meanpore diameter less than 10 nm, less than 5 nm, or less than 3 nm. Invarious embodiments, from about 0.1% to about 10%, from about 0.1% toabout 5%, from about 0.1% to about 1%, from about 1% to about 10%, orfrom about 1% to about 5% of the pore volume of the shaped porous carbonproduct, as measured by the BJH method on the basis of pores having adiameter from 1.7 nm to 100 nm, is attributable to pores having a meanpore diameter less than 10 nm, less than 5 nm, or less than 3 nm.

The shaped porous carbon products described herein are mechanicallystrong and stable. Crush strength represents the resistance of a solidto compression, and is an important property in the industrial use ofthe shaped porous carbon product as described herein. Instruments formeasuring the piece crush strength of individual solid particlesgenerally include a dynamometer that measures the force progressivelyapplied to the solid during the advancement of a piston. The appliedforce increases until the solid breaks and collapses into small piecesand eventually powder. The corresponding value of the collapsing forceis defined as piece crush strength and is typically averaged overmultiple samples. Standard protocols for measuring crush strength areknown in the art. For example, the mechanical strength of the shapedporous carbon product can be measured by piece crush strength testprotocols described by ASTM D4179 or ASTM D6175, which are incorporatedherein by reference. Some of these test methods are reportedly limitedto particles of a defined dimensional range, geometry, or method ofmanufacture. However, crush strength of irregularly shaped particles andparticles of varying dimension and manufacture may nevertheless beadequately measured by these and similar test methods.

In various embodiments, the shaped porous carbon product prepared inaccordance with the present invention has a radial piece crush strengthof greater than about 4.4 N/mm (1 lb/mm), greater than about 8.8 N/mm (2lbs/mm), or greater than about 13.3 N/mm (3 lbs/mm). In certainembodiments, the radial piece crush strength of the shaped porous carbonproduct is from about 4.4 N/mm (1 lb/mm) to about 88 N/mm (20 lbs/mm),from about 4.4 N/mm (1 lb/mm) to about 66 N/mm (15 lbs/mm), or fromabout 8.8 N/mm (2 lb/mm) to about 44 N/mm (10 lbs/mm). In radial piececrush strength measurements, the measured force is relative to thedimension of the solid perpendicular to the applied load, whichtypically can range from about 0.5 mm to about 20 mm, from about 1 mm toabout 10 mm, or from about 1.5 mm to 5 mm. For irregularly shaped porouscarbon products, the radial piece crush strength is measured by applyingthe load perpendicular to the longest dimension of the solid.

Mechanical piece crush strength can also be reported on a basis that isunitless with respect to the dimension of the shaped porous carbonproduct (e.g., for generally spherically shaped solids or solids havingapproximately equal transverse dimensions). The shaped porous carbonproduct prepared in accordance with the present invention typically hasa piece crush strength greater than about 22 N (5 lbs), greater thanabout 36 N (8 lbs), or greater than about 44 N (10 lbs). In variousembodiments, shaped porous carbon product may have a piece crushstrength from about 22 N (5 lbs) to about 88 N (20 lbs), from about 22 N(5 lbs) to about 66 N (15 lbs), or from about 33 N (7.5 lbs) to about 66N (15 lbs).

In addition to crush strength, the shaped porous carbon products alsoexhibit desirable attrition and abrasion resistance characteristics.There are several test methods suitable for determining the attritionand abrasion resistance of the shaped porous carbon products andcatalysts produced in accordance with the present disclosure. Thesemethods are a measure of the propensity of the material to produce finesin the course of transportation, handling, and use on stream.

One such method is the attrition index as determined in accordance withASTM D4058-96 (Standard Test Method for Attrition and Abrasion ofCatalysts and Catalyst Carriers), which is a measurement of theresistance of a material (e.g., extrudate or catalyst particle) toattrition wear due to the repeated striking of the particle against hardsurfaces within a specified rotating test drum and is incorporatedherein by reference. This test method is generally applicable totablets, extrudates, spheres, granules, pellets as well as irregularlyshaped particles typically having at least one dimension larger thanabout 1/16 in. (1.6 mm) and smaller than about ¾ in. (19 mm), althoughattrition measurements can also be performed on larger size materials.Variable and constant rate rotating cylinder abrasimeters designedaccording to ASTM D4058-96 are readily available. Typically, thematerial to be tested is placed in drum of the rotating test cylinderand rolled at from about 55 to about 65 RPM for about 35 minutes.Afterwards, the material is removed from test cylinder and screened on a20-mesh sieve. The percentage (by weight) of the original materialsample that remains on the 20-mesh sieve is referred to as the “percentretained.” The shaped porous carbon products (e.g., extrudates) andcatalysts prepared therefrom typically exhibit a rotating drum attritionindex as measured in accordance with ASTM D4058-96 or similar testmethod such that the percent retained is greater than about 85%, greaterthan about 90%, greater than about 92%, greater than about 95%, greaterthan about 97%, or greater than about 99% by weight. A percent retainedresult of greater than about 97% is indicative of materials withexceptional mechanical stability and robust structure particularlydesirable for industrial applications.

Abrasion loss (ABL) is an alternate measurement of the resistance of theshaped porous carbon products (e.g., extrudates) and catalysts preparedtherefrom. As with the attrition index, the results of this test methodcan be used as a measure of fines production during the handling,transportation, and use of the material. Abrasion loss is a measurementof the resistance of a material to attrition wear due to the intensehorizontal agitation of the particles within the confines of a 30-meshsieve. Typically, the material to be tested is first de-dusted on a20-mesh sieve by gently moving the sieve side-to-side at least about 20times. The de-dusted sample is weighed and then transferred to theinside of a clean, 30-mesh sieve stacked above a clean sieve pan for thecollection of fines. The complete sieve stack is then assembled onto asieve shaker (e.g., RO-Tap RX-29 sieve shaker from W.S. Tyler IndustrialGroup, Mentor, OH), covered securely and shaken for about 30 minutes.The collected fines generated are weighed and divided by the de-dustedsample weight to provide a sample abrasion loss in percent by weight.The shaped porous carbon products (e.g., extrudates) and catalystsprepared therefrom typically exhibit a horizontal agitation sieveabrasion loss of less than about 5%, less than about 3%, less than about2%, less than about 1%, less than about 0.5%, less than about 0.2%, lessthan about 0.1%, less than about 0.05%, or less than about 0.03% byweight. An abrasion loss result of less than about 2% is particularlydesired for industrial applications.

The shaped porous carbon products and methods for preparing the shapedporous carbon products of the present invention include variouscombinations of features described herein. For example, in variousembodiments, the shaped porous carbon product comprises (a) carbon blackand (b) a carbonized binder comprising a carbonization product of awater soluble organic binder, wherein the shaped porous carbon producthas a BET specific surface area from about 20 m²/g to about 500 m²/g orfrom about 25 m²/g to about 250 m²/g, a mean pore diameter greater thanabout 10 nm, a specific pore volume greater than about 0.1 cm³/g, aradial piece crush strength greater than about 4.4 N/mm (1 lb/mm), and acarbon black content of at least about 35 wt. %. In other embodiments,the shaped porous carbon product comprises a carbon agglomerate, whereinthe shaped porous carbon product has a mean diameter of at least about50 μm, a BET specific surface area from about 20 m²/g to about 500 m²/gor from about 25 m²/g to about 250 m²/g, a mean pore diameter greaterthan about 10 nm, a specific pore volume greater than about 0.1 cm³/g,and a radial piece crush strength greater than about 4.4 N/mm (1 lb/mm).

The shaped porous carbon product of the present invention may also havea low sulfur content. For example, the sulfur content of the shapedporous carbon product may be no greater than about 1 wt. % or about 0.1wt. %.

Features and characteristics including the type of carbon black, thebinder, the specific surface area, the specific pore volume, the meanpore diameter, the crush strength, attrition and abrasion resistance andthe carbon black content may be independently adjusted or modifiedwithin the ranges described herein. Also, shaped porous carbon productsmay be further defined according to characteristics described herein.

For instance, the shaped porous carbon product can comprises (a) carbonblack and (b) a carbonized binder comprising a carbonization product ofa water soluble organic binder and wherein the shaped porous carbonproduct has a BET specific surface area from about 20 m²/g to about 500m²/g, a mean pore diameter greater than about 5 nm, a specific porevolume greater than about 0.1 cm³/g, a radial piece crush strengthgreater than about 4.4 N/mm (1 lb/mm), a carbon black content of atleast about 35 wt. %, and a carbonized binder content from about 20 wt.% to about 50 wt. %.

In other embodiments, a shaped porous carbon product of the presentinvention comprises (a) carbon black and (b) a carbonized bindercomprising a carbonization product of a water soluble organic binder,wherein the shaped porous carbon product has a BET specific surface areafrom about 20 m²/g to about 500 m²/g or from about 25 m²/g to about 250m²/g, a mean pore diameter greater than about 10 nm, a specific porevolume greater than about 0.1 cm³/g, and a radial piece crush strengthgreater than about 4.4 N/mm (1 lb/mm), and a carbon black content of atleast about 35 wt. %, and wherein the shaped porous carbon product has apore volume measured on the basis of pores having a diameter from 1.7 nmto 100 nm and at least about 35% of the pore volume is attributable topores having a mean pore diameter of from about 10 nm to about 50 nm.

Yet another shaped porous carbon product of the present inventioncomprises a carbon agglomerate, wherein the shaped porous carbon producthas a mean diameter of at least about 50 μm, a BET specific surface areafrom about 20 m²/g to about 500 m²/g or from about 25 m²/g to about 250m²/g, a mean pore diameter greater than about 10 nm, a specific porevolume greater than about 0.1 cm³/g, and a radial piece crush strengthgreater than about 4.4 N/mm (1 lb/mm), and wherein the shaped porouscarbon product has a pore volume measured on the basis of pores having adiameter from 1.7 nm to 100 nm and at least about 35% of the pore volumeis attributable to pores having a mean pore diameter of from about 10 nmto about 50 nm.

Methods of the present invention include various combinations of thefeatures, characteristics, and method steps described herein. Forexample, various methods for preparing the shaped porous carbon productinclude mixing and heating water and a water soluble organic binder toform a binder solution, wherein the water and binder are heated to atemperature of at least about 50° C., and wherein the binder comprises:(i) a saccharide selected from the group consisting of a monosaccharide,a disaccharide, an oligosaccharide, a derivative thereof, and anycombination thereof and (ii) a polymeric carbohydrate, a derivative of apolymeric carbohydrate, or a non-carbohydrate synthetic polymer, or anycombination thereof; mixing carbon black particles with the bindersolution to produce a carbon black mixture; forming the carbon blackmixture to produce a shaped carbon black composite; and heating theshaped carbon black composite to carbonize the binder to a waterinsoluble state and to produce a shaped porous carbon product.

Other methods for preparing the shaped porous carbon product includemixing water, carbon black, and a water soluble organic binder to form acarbon black mixture, wherein the binder comprises: (i) a saccharideselected from the group consisting of a monosaccharide, a disaccharide,an oligosaccharide, a derivative thereof, and any combination thereofand (ii) a polymeric carbohydrate, a derivative of a polymericcarbohydrate, or a non-carbohydrate synthetic polymer, or anycombination thereof; forming the carbon black mixture to produce ashaped carbon black composite; and heating the shaped carbon blackcomposite to carbonize the binder to a water insoluble state and toproduce a shaped porous carbon product.

Further methods include mixing water, carbon black, and a binder to forma carbon black mixture, wherein the binder comprises a saccharideselected from the group consisting of a monosaccharide, a disaccharide,an oligosaccharide, a derivative thereof, or any combination thereof andwherein the weight ratio of the binder to carbon black in the carbonblack mixture is at least about 1:4, at least about 1:3, at least about1:2, at least about 1:1, or at least 1.5:1; forming the carbon blackmixture to produce a shaped carbon black composite; and heating theshaped carbon black composite to carbonize the binder to a waterinsoluble state and to produce a shaped porous carbon product.

Still other methods include mixing water, carbon black, and a binder toform a carbon black mixture, wherein the binder comprises a saccharideselected from the group consisting of a monosaccharide, a disaccharide,an oligosaccharide, a derivative thereof, or any combination thereof andwherein the water content of the carbon black mixture is no more thanabout 80% by weight, no more than about 55% by weight, no more thanabout 40% by weight, or no more than about 25% by weight; forming thecarbon black mixture to produce a shaped carbon black composite; andheating the shaped carbon black composite to carbonize the binder to awater insoluble state and to produce a shaped porous carbon product.

Another method of preparing the shaped porous carbon product byextrusion preferably comprises mixing carbon black particles with anaqueous solution comprising a water soluble organic binder compoundselected from the group consisting of a monosaccharide, a disaccharide,an oligosaccharide, a polysaccharide, and combinations thereof toproduce a carbon black mixture, wherein the carbon black mixturecomprises at least about 40 wt. % of the carbon black and at least about40 wt. % of the binder on a dry basis; forming the carbon black mixtureunder a pressure of at least 500 kPa (5 bar) to produce a shaped carbonblack composite; drying the shaped carbon black material at atemperature from about room temperature (e.g., about 20° C.) to about150° C.; and heating the dried shaped carbon black composite to atemperature between about 250° C. and about 800° C. in an oxidative,inert, or reductive atmosphere (e.g., an inert N₂ atmosphere) tocarbonize the binder to a water insoluble state and produce the shapedporous carbon product, wherein the shaped porous carbon product has amean diameter of at least about 50 μm, a BET specific surface area fromabout 20 m²/g to about 500 m²/g or from about 25 m²/g to about 250 m²/g,a mean pore diameter greater than about 10 nm, a specific pore volumegreater than about 0.1 cm³/g, and a radial crush strength greater thanabout 4.4 N/mm (1 lb/mm). Typically, the water soluble organic bindercompound is selected from the group consisting of a monosaccharide, anoligosaccharide, a polysaccharide, and combinations thereof. The carbonblack content of the shape porous carbon product can be at least about35 wt. % or as described herein. Also, in some embodiments, the shapedporous carbon product has a pore volume measured on the basis of poreshaving a diameter from 1.7 nm to 100 nm and at least about 35% of thepore volume is attributable to pores having a mean pore diameter of fromabout 10 nm to about 50 nm. The carbon black mixture may optionally beheated during the forming step (e.g., extrusion, pelletizing, pilling,tableting, cold or hot isostatic pressing, calandering, injectionmolding, 3D printing, drip casting, or other methods) to facilitate theforming of the carbon black mixture into the desired shape.

Additional shaped porous carbon products and methods of preparation ofthe present invention include any combinations of the features describedherein and where features described above are independently substitutedor added to the aforementioned embodiments.

The shaped porous carbon black products can also be wash-coated ordip-coated onto other materials to prepare structured compositematerials. The shaped porous carbon black products (at leastmicron-sized) can be domains on heterogeneous, segregated compositematerials (e.g., carbon—ZrO₂ composites or carbon domains hosted bylarge-pore (mm-sized) ceramic foams) as well as layered or structuredmaterials (e.g., carbon black wash-coats onto inert supports such assteatite, plastic or glass balls).

The shaped porous carbon black product of the invention may be furthertreated thermally or chemically to alter the physical and chemicalcharacteristics of the shaped porous carbon black product. For examplechemical treatment such as an oxidation may a produce a more hydrophilicsurface which may provide advantages for preparing a catalyst (improvedwetting and dispersion). Oxidation methods are known in the art, see forexample U.S. Pat. Nos. 7,922,805 and 6,471,763. In other embodiments,the shaped porous carbon black product has been surface treated usingknown methods for attaching a functional group to a carbon basedsubstrate. See, e.g., WO2002/018929, WO97/47691, WO99/23174, WO99/31175,WO99/51690, WO2000/022051, and WO99/63007, all of which are incorporatedherein by reference. The functional group may be an ionizable group suchthat when the shaped porous carbon black product is subjected toionizing conditions, it comprises an anionic or cationic moiety. Thisembodiment is useful when the shaped porous carbon black product is usedas a separation media in chromatography columns and other separationdevices.

Catalyst Compositions and Methods of Preparation

Various aspects of the present invention are also directed to catalystcompositions comprising the shaped porous carbon product as a catalystsupport and methods of preparing the catalyst compositions. The shapedporous carbon products of the present invention provide effectivedispersion and anchoring of catalytically active components orprecursors thereof to the surface of the carbon product. The catalystcompositions of the present invention are suitable for use in long termcontinuous flow operation phase reactions under demanding reactionconditions such as liquid phase reactions in which the shaped porouscarbon product is exposed to reactive solvents such as acids and waterat elevated temperatures. The catalyst compositions comprising theshaped porous carbon products of the present invention demonstrateoperational stability necessary for commodity applications.

In general, the catalyst compositions of the present invention comprisethe shaped porous carbon product as a catalyst support and acatalytically active component or precursor thereof at a surface of thesupport (external and/or internal surface). In various catalystcompositions of the present invention, the catalytically activecomponent or precursor thereof comprises a metal at a surface of theshaped porous carbon product. In these and other embodiments, the metalcomprises at least one metal selected from groups IV, V, VI, VII, VIII,IX, X, XI, XII, and XIII. Some preferred metals include cobalt, nickel,copper, zinc, iron, vanadium, molybdenum, manganese, barium, ruthenium,rhodium, rhenium, palladium, silver, osmium, iridium, platinum, gold,and combinations thereof. In various embodiments, the metal comprises atleast one d-block metal. Some preferred d-block metals are selected fromthe group consisting of cobalt, nickel, copper, zinc, iron, ruthenium,rhodium, palladium, silver, osmium, iridium, platinum, gold andcombinations thereof. Typically, the metal(s) at a surface of thecatalyst support may constitute f from about 0.1% to about 50%, fromabout 0.1% to about 25%, from about 0.1% to about 10%, from about 0.1%to about 5%, from about 0.25% to about 50%, from about 0.25% to about25%, from about 0.25% to about 10%, from about 0.25% to about 5%, fromabout 1% to about 50%, from about 1% to about 25%, from about 1% toabout 10%, from about 1% to about 5%, from about 5% to about 50%, fromabout 5% to about 25%, or from about 5% to about 10% of the total weightof the catalyst.

In general, the metals may be present in various forms (e.g., elemental,metal oxide, metal hydroxides, metal ions, metalates, polyanions,oligomers or colloidal etc.). Typically, however, the metals are reducedto elemental form during preparation of the catalyst composition orin-situ in the reactor under reaction conditions.

The metal(s) may be deposited on a surface of the shaped porous carbonproduct according procedures known in the art including, but not limitedto incipient wetness, ion-exchange, deposition-precipitation, coatingand vacuum impregnation. When two or more metals are deposited on thesame support, they may be deposited sequentially or simultaneously.Multiple impregnation steps are also possible (e.g., dual impregnationof the same metal under different conditions to increase overall metalloading or tune the metal distribution across the shell). In variousembodiments, the metal(s) deposited on the shaped porous carbon productfor the oxidation catalyst form a shell at least partially covering thesurface of the carbon product. In other words, metal deposited on theshaped porous carbon product coats external surfaces of the carbonproduct. In various embodiments, the metal penetrates surficial pores ofthe shaped porous carbon product to form a shell layer (“egg shell”)with a thickness of from about 10 μm to about 400 μm, or from about 50μm to about 150 μm (e.g., about 100 μm). In certain embodiments theshell may be produced sub-surface to produce a 10 μm to about 400 μmsub-surface band containing the catalytically active metals (“eggyolk”). Also structured shells featuring different metal distributionsacross the shell for the various metals are possible.

In other embodiments, the metal(s) may be deposited on the carbon blackparticles before forming the shaped porous carbon product. Accordingly,in these embodiments, the carbon black mixture may further comprise ametal, such as, for example, a d-block metal. Some preferred d-blockmetals are selected from the group consisting of cobalt, nickel, copper,zinc, iron, ruthenium, rhodium, palladium, silver, osmium, iridium,platinum, gold and combinations thereof. In various embodiments, themetal comprises at least one metal selected from groups IV, V, VI, VII,VIII, IX, X, XI, XII, and XIII. Preferred metals include cobalt, nickel,copper, zinc, iron, vanadium, molybdenum, manganese, barium, ruthenium,rhodium, rhenium, palladium, silver, osmium, iridium, platinum, gold,and combinations thereof. Typically, the metal(s) may constitute fromabout 0.1% to about 50%, from about 0.1% to about 25%, from about 0.1%to about 10%, from about 0.1% to about 5%, from about 0.25% to about50%, from about 0.25% to about 25%, from about 0.25% to about 10%, fromabout 0.25% to about 5%, from about 1% to about 50%, from about 1% toabout 25%, from about 1% to about 10%, from about 1% to about 5%, fromabout 5% to about 50%, from about 5% to about 25%, or from about 5% toabout 10%. For example, when the metal used is a noble metal, the metalcontent can be from about 0.25% to about 10% of the total weight of theshaped porous carbon product. Alternatively, when the metal used is anon-noble metal, the metal content can be from about 0.1% to about 50%of the total weight of the shaped porous carbon product.

In various embodiments, following metal deposition, the catalystcomposition is optionally dried, for example, at a temperature of atleast about 50° C., more typically at least about 120° C. for a periodof time of at least about 1 hour, more typically 3 hours or more.Alternatively, the drying may be conducted in a continuous or stagedmanner where independently controlled temperature zones (e.g., 60° C.,80° C., and 120° C.) are utilized. Typically, drying is initiated belowthe boiling point of the solvent, e.g., 60° C. and then increased. Inthese and other embodiments, the catalyst is dried under sub-atmosphericor atmospheric pressure conditions. In various embodiments, the catalystis reduced after drying (e.g., by flowing 5% H₂ in N₂ at 350° C. for 3hours). Still further, in these and other embodiments, the catalyst iscalcined, for example, at a temperature of at least about 200° C. for aperiod of time (e.g., at least about 3 hours).

In some embodiments, the catalyst composition of the present inventionis prepared by depositing the catalytically active component orprecursor thereof subsequent to forming the shaped porous carbon product(i.e., depositing directly on a surface of the shaped porous carbonproduct). The catalyst composition of the present invention can beprepared by contacting the shaped porous carbon product with asolubilized metal complex or combination of solubilized metal complexes.The heterogeneous mixture of solid and liquids can then be stirred,mixed and/or shaken to enhance the uniformity of dispersion of thecatalyst, which, in turn, enables the more uniform deposition ofmetal(s) on the surface of the support upon removal of the liquids.Following deposition, the metal complex(es) on the shaped porous carbonproducts are heated and reduced under a reducing agent such as ahydrogen containing gas (e.g., forming gas 5% H₂ and 95% N₂). Thetemperature at which the heating is conducted generally ranges fromabout 150° C. to about 600° C., from about 200° C. to about 500° C., orfrom about 100° C. to about 400° C. Heating is typically conducted for aperiod of time ranging from about 1 hour to about 5 hours or from about2 hour to about 4 hours. Reduction may also be carried in the liquidphase. For example, catalyst compositions can be treated in a fixed bedwith the liquid containing a reducing agent pumped through the staticcatalyst.

In other embodiments, the catalyst composition of the present inventionis prepared by depositing the catalytically active component orprecursor thereof on carbon black prior to forming the shaped porouscarbon product. In one such method, a slurry of carbon black withsolubilized metal complex(es) is prepared. Carbon black may be initiallydispersed in a liquid such as water. Thereafter, the solubilized metalcomplex(es) may be added to the slurry containing the carbon black. Theheterogeneous mixture of solid and liquids can then be stirred, mixedand/or shaken to enhance the uniformity of dispersion of the catalyst,which, in turn, enables the more uniform deposition of metal(s) on thesurface of the carbon black upon removal of the liquids. Followingdeposition, the metal complex(es) on the carbon black are heated andreduced with a reducing agent as described above. The metal-loadedcarbon black particles can then be formed according to the methoddescribed for the shaped porous carbon product. The slurry can also bewash-coated onto inert supports rather than shaped into bulk catalystpellets.

The catalyst compositions comprising the shaped porous carbon product asa catalyst support can be deployed in various reactor formats,particularly those suited liquid phase medium such as batch slurry,continuous slurry-based stirred tank reactors, cascade of stirred tankreactors, bubble slurry reactor, fixed beds, ebulated beds and otherknown industrial reactor formats. Accordingly, in various aspects, thepresent invention is further directed to methods of preparing a reactorvessel for a liquid phase catalytic reaction. In other aspects, thepresent invention is further directed to methods of preparing a reactorvessel for a gaseous phase catalytic reaction. The method comprisescharging the reactor vessel with a catalyst composition comprising theshaped porous carbon product as described herein as a catalyst support.In some embodiments, the reactor vessel is a fixed bed reactor.

Various methods for preparing a catalyst composition in accordance withthe present invention include mixing and heating water and a watersoluble organic binder to form a binder solution, wherein the water andbinder are heated to a temperature of at least about 50° C., and whereinthe binder comprises: (i) a saccharide selected from the groupconsisting of a monosaccharide, a disaccharide, an oligosaccharide, aderivative thereof, and any combination thereof and (ii) a polymericcarbohydrate, a derivative of a polymeric carbohydrate, or anon-carbohydrate synthetic polymer, or any combination thereof; mixingcarbon black particles with the binder solution to produce a carbonblack mixture; forming the carbon black mixture to produce a shapedcarbon black composite; heating the shaped carbon black composite tocarbonize the binder to a water insoluble state and to produce a shapedporous carbon product; and depositing a catalytically active componentor precursor thereof on the shaped porous carbon product to produce thecatalyst composition.

Other methods include mixing water, carbon black, and a water solubleorganic binder to form a carbon black mixture, wherein the bindercomprises: (i) a saccharide selected from the group consisting of amonosaccharide, a disaccharide, an oligosaccharide, a derivativethereof, and any combination thereof and (ii) a polymeric carbohydrate,a derivative of a polymeric carbohydrate, or a non-carbohydratesynthetic polymer, or any combination thereof; forming the carbon blackmixture to produce a shaped carbon black composite; heating the shapedcarbon black composite to carbonize the binder to a water insolublestate and to produce a shaped porous carbon product; and depositing acatalytically active component or precursor thereof on the shaped porouscarbon product to produce the catalyst composition.

Further methods for preparing a catalyst composition in accordance withthe present invention include mixing water, carbon black, and a binderto form a carbon black mixture, wherein the binder comprises asaccharide selected from the group consisting of a monosaccharide, adisaccharide, an oligosaccharide, a derivative thereof, or anycombination thereof and wherein the weight ratio of the binder to carbonblack in the carbon black mixture is at least about 1:4, at least about1:3, at least about 1:2, at least about 1:1, or at least 1.5:1; formingthe carbon black mixture to produce a shaped carbon black composite;heating the shaped carbon black composite to carbonize the binder to awater insoluble state and to produce a shaped porous carbon product; anddepositing a catalytically active component or precursor thereof on theshaped porous carbon product to produce the catalyst composition.

Other methods include mixing water, carbon black, and a binder to form acarbon black mixture, wherein the binder comprises a saccharide selectedfrom the group consisting of a monosaccharide, a disaccharide, anoligosaccharide, a derivative thereof, or any combination thereof andwherein the water content of the carbon black mixture is no more thanabout 80% by weight, no more than about 55% by weight, no more thanabout 40% by weight, or no more than about 25% by weight; forming thecarbon black mixture to produce a shaped carbon black composite; heatingthe shaped carbon black composite to carbonize the binder to a waterinsoluble state and to produce a shaped porous carbon product; anddepositing a catalytically active component or precursor thereof on theshaped porous carbon product to produce the catalyst composition.

Still further methods include depositing a catalytically activecomponent or precursor thereof on a shaped porous carbon product toproduce the catalyst composition, wherein the shaped porous carbonproduct comprises: (a) carbon black and (b) a carbonized bindercomprising a carbonization product of a water soluble organic binder andwherein the shaped porous carbon product has a BET specific surface areafrom about 20 m²/g to about 500 m²/g, a mean pore diameter greater thanabout 5 nm, a specific pore volume greater than about 0.1 cm³/g, aradial piece crush strength greater than about 4.4 N/mm (1 lb/mm), acarbon black content of at least about 35 wt. %, and a carbonized bindercontent from about 20 wt. % to about 50 wt. %.

Catalytic Processes

The catalyst compositions comprising the shaped porous carbon product ofthe present invention are useful for various catalytic conversionsincluding oxidations, reductions, dehydrations, hydrogenations and otherknown transformations using appropriate active metals formulations andwhich can be conducted in gaseous or liquid medium. Accordingly, infurther aspects, the present invention is directed to processes for thecatalytic conversion of a reactant.

Processes of the present invention comprise contacting a liquid mediumcomprising the reactant with a catalyst composition comprising theshaped porous carbon product as a catalyst support. In variousembodiments, the shaped porous carbon product comprises (a) carbon blackand (b) a carbonized binder comprising a carbonization product of awater soluble organic binder, wherein the shaped porous carbon producthas a BET specific surface area from about 20 m²/g to about 500 m²/g orfrom about 25 m²/g to about 250 m²/g, a mean pore diameter greater thanabout 10 nm, a specific pore volume greater than about 0.1 cm³/g, aradial piece crush strength greater than about 4.4 N/mm (1 lb/mm), and acarbon black content of at least about 35 wt. %. In other embodiments,the shaped porous carbon product comprises a carbon agglomerate, whereinthe shaped porous carbon product has a mean diameter of at least about50 μm, a BET specific surface area from about 20 m²/g to about 500 m²/gor from about 25 m²/g to about 250 m²/g, a mean pore diameter greaterthan about 10 nm, a specific pore volume greater than about 0.1 cm³/g,and a radial piece crush strength greater than about 4.4 N/mm (1 lb/mm).Typically, the catalyst composition has superior mechanical strength(e.g., mechanical piece crush strength and/or radial piece crushstrength) and is stable to the continuous flow of the liquid medium andreaction conditions for at least about 500 hours or about 1,000 hourswithout substantial loss in catalytic productivity, selectivity, and/oryield.

In addition, it has been surprisingly discovered that the catalystcompositions comprising the shaped porous carbon product of the presentinvention are highly productive and selective catalysts for a certain ofchemical transformations such as the conversion of highly functionalizedand/or non-volatile molecules including, but not limited tobiorenewably-derived molecules and intermediates for commodityapplications.

Catalytic Oxidation

One series of chemical transformations that the catalyst compositions ofthe present invention are suited for is the selective oxidation of ahydroxyl group to a carboxyl group in a liquid or gaseous reactionmedium. For example, one series of chemical transformations that thecatalyst compositions of the present invention are especially suited foris the selective oxidation an aldose to an aldaric acid. Accordingly,catalyst compositions of the present invention as described herein canbe utilized as oxidation catalysts. Aldoses include, for example,pentoses and hexoses (i.e., C-5 and C-6 monosaccharides). Pentosesinclude ribose, arabinose, xylose, and lyxose, and hexoses includeglucose, allose, altrose, mannose, gulose, idose, galactose, and talose.Accordingly, in various embodiments, the present invention is alsodirected to a process for the selective oxidation of an aldose to analdaric acid comprising reacting the aldose with oxygen in the presenceof a catalyst composition as described herein to form the aldaric acid.Typically, the catalyst composition comprises at least platinum as acatalytically active component.

The catalyst compositions of the present invention have been found to beespecially selective for the oxidation of the glucose to glucaric acid.Accordingly, the present invention is directed to a process for theselective oxidation of glucose to glucaric acid comprising reacting thealdose with oxygen in the presence of a catalyst composition asdescribed herein to form glucaric acid. U.S. Pat. No. 8,669,397, theentire contents of which are incorporated herein by reference, disclosesvarious catalytic processes for the oxidation of glucose to glucaricacid. In general, glucose may be converted to glucaric acid in highyield by reacting glucose with oxygen (e.g., air, oxygen-enriched air,oxygen alone, or oxygen with other constituents substantially inert tothe reaction) in the presence of an oxidation catalyst according to thefollowing reaction:

The oxidation can be conducted in the absence of added base (e.g., KOH)or where the initial pH of the reaction medium and/or the pH of reactionmedium at any point in the reaction is no greater than about 7, nogreater than 7.0, no greater than about 6.5, or no greater than about 6.The initial pH of the reaction mixture is the pH of the reaction mixtureprior to contact with oxygen in the presence of an oxidation catalyst.In fact, catalytic selectivity can be maintained to attain glucaric acidyield in excess of about 30%, about 40%, about 50%, about 60% and, insome instances, attain yields in excess of 65% or higher. The absence ofadded base advantageously facilitates separation and isolation of theglucaric acid, thereby providing a process that is more amenable toindustrial application, and improves overall process economics byeliminating a reaction constituent. The “absence of added base” as usedherein means that base, if present (for example, as a constituent of afeedstock), is present in a concentration which has essentially noeffect on the efficacy of the reaction; i.e., the oxidation reaction isbeing conducted essentially free of added base. The oxidation reactioncan also be conducted in the presence of a weak carboxylic acid, such asacetic acid, in which glucose is soluble. The term “weak carboxylicacid” as used herein means any unsubstituted or substituted carboxylicacid having a pKa of at least about 3.5, more preferably at least about4.5 and, more particularly, is selected from among unsubstituted acidssuch as acetic acid, propionic acid or butyric acid, or mixturesthereof.

The oxidation reaction may be conducted under increased oxygen partialpressures and/or higher oxidation reaction mixture temperatures, whichtends to increase the yield of glucaric acid when the reaction isconducted in the absence of added base or at a pH below about 7.Typically, the partial pressure of oxygen is at least about 15 poundsper square inch absolute (psia) (104 kPa), at least about 25 psia (172kPa), at least about 40 psia (276 kPa), or at least about 60 psia (414kPa). In various embodiments, the partial pressure of oxygen is up toabout 1,000 psia (6895 kPa), more typically in the range of from about15 psia (104 kPa) to about 500 psia (3447 kPa), from about 75 psia (517kPa) to about 500 psia (3447 kPa), from about 100 psia (689 kPa) toabout 500 psia (3447 kPa), from about 150 psia (1034 kPa) to about 500psia (3447 kPa). Generally, the temperature of the oxidation reactionmixture is at least about 40° C., at least about 60° C., at least about70° C., at least about 80° C., at least about 90° C., at least about100° C., or higher. In various embodiments, the temperature of theoxidation reaction mixture is from about 40° C. to about 200° C., fromabout 60° C. to about 200° C., from about 70° C. to about 200° C., fromabout 80° C. to about 200° C., from about 80° C. to about 180° C., fromabout 80° C. to about 150° C., from about 90° C. to about 180° C., orfrom about 90° C. to about 150° C. Surprisingly, the catalystcompositions comprising the shaped porous carbon product as a catalystsupport permit glucose oxidation at elevated temperatures (e.g., fromabout 100° C. to about 160° C. or from about 125° C. to about 150° C.)without heat degradation of the catalyst. In particular, reactor formatssuch as a fixed bed reactor which can provide a relatively high liquidthroughput in combination with the catalyst compositions comprising theshaped porous carbon product comprising carbon black have been found topermit oxidation at temperatures in excess of 140° C. (e.g., 140° toabout 150° C.).

Oxidation of glucose to glucaric acid can also be conducted in theabsence of nitrogen as an active reaction constituent. Some processesemploy nitrogen compounds such as nitric acid as an oxidant. The use ofnitrogen in a form in which it is an active reaction constituent, suchas nitrate or nitric acid, results in the need for NO_(x) abatementtechnology and acid regeneration technology, both of which addsignificant cost to the production of glucaric acid from these knownprocesses, as well as providing a corrosive environment which maydeleteriously affect the equipment used to carry out the process. Bycontrast, for example, in the event air or oxygen-enriched air is usedin the oxidation reaction of the present invention as the source ofoxygen, the nitrogen is essentially an inactive or inert constituent.Thus, an oxidation reaction employing air or oxygen-enriched air is areaction conducted essentially free of nitrogen in a form in which itwould be an active reaction constituent.

In accordance with various embodiments, glucose is oxidized to glucaricacid in the presence of a catalyst composition comprising the shapedporous carbon product as a catalyst support described herein and acatalytically active component at a surface of the support. In certainembodiments the catalytically active component comprises platinum. Insome embodiments, the catalytically active component comprises platinumand gold.

Applicants have discovered that oxidation catalyst compositionscomprising the shaped porous carbon product of the present inventionprovide unexpectedly greater selectivity and yield for producingglucaric acid from glucose when compared to similar catalysts comprisingsimilar support materials such as activated carbon. In particular,applicants have unexpectedly found that enhanced selectivity and yieldfor glucaric acid can be achieved by use of an oxidation catalystcomposition comprising the shaped porous carbon product as a catalystsupport and a catalytically active component comprising platinum andgold at a surface of the shaped porous carbon product (i.e., at asurface of the catalyst support).

The oxidation catalyst can include any of the shaped porous carbonproducts as described herein. For example, in various embodiments, theshaped porous carbon product comprises (a) carbon black and (b) acarbonized binder comprising a carbonization product of a water solubleorganic binder, wherein the shaped porous carbon product has a BETspecific surface area from about 20 m²/g to about 500 m²/g or from about25 m²/g to about 250 m²/g, a mean pore diameter greater than about 10nm, a specific pore volume greater than about 0.1 cm³/g, a radial piececrush strength greater than about 4.4 N/mm (1 lb/mm), and a carbon blackcontent of at least about 35 wt. %. In other embodiments, the shapedporous carbon product comprises a carbon agglomerate, wherein the shapedporous carbon product has a mean diameter of at least about 50 μm, a BETspecific surface area from about 20 m²/g to about 500 m²/g or from about25 m²/g to about 250 m²/g, a mean pore diameter greater than about 10nm, a specific pore volume greater than about 0.1 cm³/g, and a radialpiece crush strength greater than about 4.4 N/mm (1 lb/mm). Anothershaped porous carbon product in accordance with the present inventionalso has a pore volume measured on the basis of pores having a diameterfrom 1.7 nm to 100 nm and at least about 35% of the pore volume isattributable to pores having a mean pore diameter of from about 10 nm toabout 50 nm.

The enhanced glucaric acid yield is typically at least about 30%, atleast about 35%, at least about 40%, at least about, 45%, or at leastabout 50% (e.g., from about 35% to about 65%, from about 40% to about65%, or from about 45% to about 65%). Further, the enhanced glucaricacid selectivity is typically at least about 70%, at least about 75%, orat least about 80%.

In various embodiments, the catalytically active components orprecursors thereof comprising platinum and gold are in the formdescribed in U.S. Patent Application Publication 2011/0306790, theentire contents of which are incorporated herein by reference. Thispublication describes various oxidation catalysts comprising acatalytically active component comprising platinum and gold, which areuseful for the selective oxidation of compositions comprised of aprimary alcohol group and at least one secondary alcohol group (e.g.,glucose).

In various embodiments, an oxidation catalyst composition according thepresent invention comprises the shaped porous carbon product asdescribed herein as a catalyst support comprising particles of gold inthe form of a gold-containing alloy and particles consisting essentiallyof platinum (0) as the catalytically active components on a surface ofthe catalyst support. Typically, the total metal loading of the catalystcomposition is about 10 wt. % or less, from about 1 wt. % to about 8 wt.%, from about 1 wt. % to about 5 wt. %, or from about 2 wt. % to about 4wt. %.

In order to oxidize glucose to glucaric acid, a sufficient amount of thecatalytically active component must be present relative to the amount ofreactant (i.e., glucose). Accordingly, in a process of the presentinvention for the oxidation of glucose to glucaric acid as describedherein where the catalytically active component comprises platinum,typically the mass ratio of glucose to platinum is from about 10:1 toabout 1000:1, from about 10:1 to about 500:1, from about 10:1 to about200:1, or from about 10:1 to about 100:1.

In various embodiments, the oxidation catalyst of the present inventionmay be prepared according to the following method. The gold component ofthe catalyst is typically added to the shaped porous carbon product as asolubilized constituent to enable the formation of a uniform suspension.A base is then added to the suspension in order to create an insolublegold complex which can be more uniformly deposited onto the support. Forexample, the solubilized gold constituent is provided to the slurry asgold salt, such as HAuCl4. Upon creation of a well dispersed,heterogeneous mixture, a base is added to the slurry to form aninsoluble gold complex which then deposits on the surface of the shapedporous carbon product. Although any base which can affect the formationof an insoluble gold complex is useable, bases such as KOH, NaOH aretypically employed. It may be desirable, though not required, to collectthe shaped porous carbon product on which has been deposited theinsoluble gold complex prior to adding the platinum-containingconstituent, which collection can readily be accomplished by any of avariety of means known in the art such as, for example, centrifugation.The collected solids may optionally be washed and then may be heated todry. Heating may also be employed so as to reduce the gold complex onthe support to gold (0). Heating may be conducted at temperaturesranging from about 60° C. (to dry) up to about 500° C. (at whichtemperature the gold can be effectively reduced). In variousembodiments, the heating step may be conducted in the presence of areducing or oxidizing atmosphere in order to promote the reduction ofthe complex to deposit the gold onto the support as gold (0). Heatingtimes vary depending upon, for example, the objective of the heatingstep and the decomposition rate of the base added to form the insolublecomplex, and the heating times can range from a few minutes to a fewdays. More typically, the heating time for the purpose of drying rangesfrom about 2 to about 24 hours and for reducing the gold complex is onthe order of about 1 to about 4 hours.

In various embodiments, the concentration of the shaped porous carbonproduct in the slurry can be in the range of about 1 to about 100 g ofsolid/liter of slurry, and in other embodiments the concentration can bein the range of about 5 to about 25 g of solid/liter of slurry.

Mixing of the slurry containing the soluble gold-containing compound iscontinued for a time sufficient to form at least a reasonably uniformsuspension. Appropriate times can range from minutes to a few hours.After addition of the base to convert the gold-containing compound to aninsoluble gold-containing complex, the uniformity of the slurry shouldbe maintained for a time sufficient to enable the insoluble complex tobe formed and deposit on the shaped porous carbon product. In variousembodiments, the time can range from a few minutes to several hours.

Platinum can be added to the shaped porous carbon product or slurrythereof after deposition of gold onto the shaped porous carbon productor after heat treatment to reduce the gold complex on the support togold (0). Alternatively, the platinum may be added to the shaped porouscarbon product or slurry thereof prior to the addition of thesolubilized gold compound provided the platinum present on the supportis in a form that will not be re-dissolved upon the addition of baseused to promote the deposition of gold onto the support. The platinum istypically added as a solution of a soluble precursor or as a colloid.Platinum may be added as a compound selected form the group of platinum(II) nitrate, platinum(IV) nitrate, platinum oxynitrate, platinum (II)acetylacetonate (acac), tetraamineplatinum (II) nitrate,tetraamineplatinum (II) hydrogenphosphate, tetraamineplatinum (II)hydrogencarbonate, tetraamineplatinum (II) hydroxide, H2PtCl6, PtCl4,Na2PtCl4, K2PtCl4, (NH4)2PtCl4, Pt(NH3)4Cl2, mixed Pt(NH3)xCly,K2Pt(OH)6, Na2Pt(OH)6, (NMe4)2Pt(OH)6, and (EA)2Pt(OH)6 whereEA=ethanolamine. More preferred compounds include platinum(II) nitrate,platinum(IV) nitrate, platinum(II) acetylacetonate (acac), tetraamineplatinum(II) hydroxide, K2PtCl4, and K2Pt(OH)6.

Subsequent to the addition of the platinum compound, the support slurryand platinum-containing compound is dried. Drying may be conducted atroom temperature or at a temperature up to about 120° C. Morepreferably, drying is conducted at a temperature in the range of about40° C. to about 80° C. and more preferably still at about 60° C. Thedrying step may be conducted for a period of time ranging from about afew minutes to a few hours. Typically, the drying time is in the rangeof about 6 hours to about 24 hours. The drying can also be done withcontinuous or staged temperature increase from about 60° C. to 120° C.on a band calciner or belt dryer (which is preferred for commercialapplications).

After drying the support having the platinum compound deposited thereon,it is subjected to at least one thermal treatment in order to reduceplatinum deposited as platinum (II) or platinum (IV) to platinum (0).The thermal treatment(s) can be conducted in air or in any reducing oroxidizing atmosphere. In various embodiments the thermal treatment(s) is(are) conducted under a forming gas atmosphere. Alternatively, a liquidreducing agent may be employed to reduce the platinum; for example,hydrazine or formaldehyde or formic acid or salts thereof (e.g., sodiumformate) or NaH2PO2 may be employed to effect the requisite reduction ofthe platinum. The atmosphere under which the thermal treatment isconducted is dependent upon the platinum compound employed, with theobjective being substantially converting the platinum on the support toplatinum (0).

The temperatures at which the thermal treatment(s) is (are) conductedgenerally range from about 150° C. to about 600° C. More typically, thetemperatures of the thermal treatment(s) range from about 200° C. toabout 500° C. and, preferably, the range is from about 200° C. to about400° C. The thermal treatment is typically conducted for a period oftime ranging from about 1 hour to about 8 hours or from about 1 hour toabout 3 hours.

In various embodiments, the metal(s) deposited on the shaped porouscarbon product for the oxidation catalyst form a shell at leastpartially covering the surface of the carbon product. In other words,metal deposited on the shaped porous carbon product coats externalsurfaces of the carbon product. In various embodiments, the metalpenetrates surficial pores of the shaped porous carbon product to form ashell layer (“egg shell”) with a thickness of from about 10 μm to about400 μm, or from about 50 μm to about 150 μm (e.g., about 100 μm). Incertain embodiments the shell may be produced sub-surface to produce a10 μm to about 400 μm sub-surface band containing the catalyticallyactive metals (“egg yolk”).

Catalytic Hydrodeoxygenation

One series of chemical transformations that the catalyst compositions ofthe present invention are suited for is the hydrodeoxygenation ofcarbon-hydroxyl groups to carbon-hydrogen groups in a liquid or gaseousreaction medium. For example, one series of chemical transformation thatthe catalyst compositions of the present invention are especially suitedfor is the selective halide-promoted hydrodeoxygenation of an aldaricacid or salt, ester, or lactone thereof to a dicarboxylic acid.Accordingly, catalyst compositions of the present invention as describedherein can be utilized as hydrodeoxygenation catalysts. As such, thepresent invention is also directed to a process for the selective halidepromoted hydrodeoxygenation of an aldaric acid comprising reacting thealdaric acid or salt, ester, or lactone thereof with hydrogen in thepresence of a halogen-containing compound and a catalyst composition asdescribed herein to form a dicarboxylic acid. Typically, the catalystcomposition comprises at least one noble metal as a catalytically activecomponent.

The catalyst compositions of the present invention have been found to beespecially selective for halide-promoted hydrodeoxygenation of glucaricacid or salt, ester, or lactone thereof to adipic acid. U.S. Pat. No.8,669,397, referenced above and incorporated herein by reference,describes the chemocatalytic processes for the hydrodeoxygenation ofglucaric acid to adipic acid.

Adipic acid or salts and esters thereof may be prepared by reacting, inthe presence of a hydrodeoxygenation catalyst and a halogen source,glucaric acid or salt, ester, or lactone thereof, and hydrogen,according to the following reaction:

In the above reaction, glucaric acid or salt, ester, or lactone thereofis converted to an adipic acid product by catalytic hydrodeoxygenationin which carbon-hydroxyl groups are converted to carbon-hydrogen groups.In various embodiments, the catalytic hydrodeoxygenation ishydroxyl-selective wherein the reaction is completed without substantialconversion of the one or more other non-hydroxyl functional group of thesubstrate.

The halogen source may be in a form selected from the group consistingof ionic, molecular, and mixtures thereof. Halogen sources includehydrohalic acids (e.g., HCl, HBr, HI and mixtures thereof; preferablyHBr and/or HI), halide salts, (substituted or unsubstituted) alkylhalides, or molecular (diatomic) halogens (e.g., chlorine, bromine,iodine or mixtures thereof preferably bromine and/or iodine). In variousembodiments the halogen source is in diatomic form, hydrohalic acid, orhalide salt and, more preferably, diatomic form or hydrohalic acid. Incertain embodiments, the halogen source is a hydrohalic acid, inparticular hydrogen bromide.

Generally, the molar ratio of halogen to the glucaric acid or salt,ester, or lactone thereof is about equal to or less than about 1. Invarious embodiments, the mole ratio of halogen to the glucaric acid orsalt, ester, or lactone thereof is typically from about 1:1 to about0.1:1, more typically from about 0.7:1 to about 0.3:1, and still moretypically about 0.5:1.

Generally, the reaction allows for recovery of the halogen source andcatalytic quantities (where molar ratio of halogen to the glucaric acidor salt, ester, or lactone thereof is less than about 1) of halogen canbe used, recovered and recycled for continued use as a halogen source.

Generally, the temperature of the hydrodeoxygenation reaction mixture isat least about 20° C., typically at least about 80° C., and moretypically at least about 100° C. In various embodiments, the temperatureof the hydrodeoxygenation reaction is conducted in the range of fromabout 20° C. to about 250° C., from about 80° C. to about 200° C., fromabout 120° C. to about 180° C., or from about 140° C. to 180° C.Typically, the partial pressure of hydrogen is at least about 25 psia(172 kPa), more typically at least about 200 psia (1379 kPa) or at leastabout 400 psia (2758 kPa). In various embodiments, the partial pressureof hydrogen is from about 25 psia (172 kPa) to about 2500 psia (17237kPa), from about 200 psia (1379 kPa) to about 2000 psia (13790 kPa), orfrom about 400 psia (2758 kPa) to about 1500 psia (10343 kPa).

The hydrodeoxygenation reaction is may be conducted in the presence of asolvent. Solvents suitable for the selective hydrodeoxygenation reactioninclude water and carboxylic acids, amides, esters, lactones,sulfoxides, sulfones and mixtures thereof. Preferred solvents includewater, mixtures of water and weak carboxylic acid, and weak carboxylicacid. A preferred weak carboxylic acid is acetic acid.

Applicants have discovered that hydrodeoxygenation catalyst compositionscomprising the shaped porous carbon product of the present inventionprovide enhanced selectivity and yield for producing adipic acid. Inparticular, applicants have unexpectedly found that enhanced selectivityand yield for adipic acid can be achieved by use of a catalystcomposition comprising the shaped porous carbon product of the presentinvention as a catalyst support and a catalytically active component ata surface of the shaped porous carbon product (i.e., at a surface of thecatalyst support).

The catalyst can include any of the shaped porous carbon products asdescribed herein. For example, in various embodiments, the shaped porouscarbon product comprises (a) carbon black and (b) a carbonized bindercomprising a carbonization product of a water soluble organic binder,wherein the shaped porous carbon product has a BET specific surface areafrom about 20 m²/g to about 500 m²/g or from about 25 m²/g to about 250m²/g, a mean pore diameter greater than about 5 nm, a specific porevolume greater than about 0.1 cm³/g, a radial piece crush strengthgreater than about 4.4 N/mm (1 lb/mm), and a carbon black content of atleast about 35 wt. %. In other embodiments, the shaped porous carbonproduct comprises a carbon agglomerate, wherein the shaped porous carbonproduct has a mean diameter of at least about 50 μm, a BET specificsurface area from about 20 m²/g to about 500 m²/g or from about 25 m²/gto about 250 m²/g, a mean pore diameter greater than about 5 nm, aspecific pore volume greater than about 0.1 cm³/g, and a radial piececrush strength greater than about 4.4 N/mm (1 lb/mm). Another shapedporous carbon product in accordance with the present invention also hasa pore volume measured on the basis of pores having a diameter from 1.7nm to 100 nm and at least about 35% of the pore volume is attributableto pores having a mean pore diameter of from about 10 nm to about 50 nm.

The catalytically active component or precursor thereof may includenoble metals selected from the group consisting of ruthenium, rhodium,palladium, platinum, and combinations thereof. In various embodiments,the hydrodeoxygenation catalyst comprises two or more metals. Forexample, in some embodiments, the first metal is selected from the groupconsisting of cobalt, nickel, ruthenium, rhodium, palladium, osmium,iridium, and platinum (more particularly, ruthenium, rhodium, palladium,and platinum) and the second metal is selected from the group consistingof titanium, vanadium, chromium, manganese, iron, cobalt, nickel,copper, molybdenum, ruthenium, rhodium, palladium, silver, tungsten,iridium, platinum, and gold (more particularly, molybdenum, ruthenium,rhodium, palladium, iridium, platinum, and gold). In select embodiments,the first metal is selected from the group of platinum, rhodium andpalladium, and the second metal is selected from the group consisting ofruthenium, rhodium, palladium, platinum, and gold. In certainembodiments, the first metal is platinum and the second metal isrhodium. In these and other embodiments, the platinum to rhodium molarratio of the catalyst composition of the present invention is in therange of from about 3:1 to about 1:2 or from about 3:1 to about 1:1.

In various embodiments, the metal(s) deposited on the shaped porouscarbon product for the hydrodeoxygenation catalyst form a shell at leastpartially covering the surface of the carbon product. In other words,metal deposited on the shaped porous carbon product coats externalsurfaces of the carbon product. In various embodiments, the metalpenetrates surficial pores of the shaped porous carbon product to form ashell layer (“egg shell”) with a thickness of from about 10 μm to about400 μm, or from about 50 μm to about 150 μm (e.g., about 100 μm). Incertain embodiments the shell may be produced sub-surface to produce a10 μm to about 400 μm sub-surface band containing the catalyticallyactive metals (“egg yolk”).

Hydrodeoxygenation of 1,2,6-Hexanetriol

Another chemical transformation that the catalyst compositions of thepresent invention is advantageous for is the selectivehydrodeoxygenation of 1,2,6-hexanetriol to 1,6-hexanediol (HDO) and1,2,5,6-hexanetetraol to 1,6-HDO). Accordingly, one process of thepresent invention is directed to the selective hydrodeoxygenation of1,2,6-hexanetriol comprising reacting 1,2,6-hexanetriol with hydrogenthe presence of a catalyst composition as disclosed herein to form HDO.In embodiments of this process, the catalytically active component ofthe catalyst composition comprises platinum. In some embodiments, thecatalytically active component of the catalyst composition comprisesplatinum and at least one metal (M2) selected from the group ofmolybdenum, lanthanum, samarium, yttrium, tungsten, and rhenium. Incertain embodiments, the catalytically active component of the catalystcomposition comprises platinum and tungsten.

Typically, the total weight of metal(s) is from about 0.1% to about 10%,or from 0.2% to 10%, or from about 0.2% to about 8%, or from about 0.2%to about 5%, of the total weight of the catalyst. In more preferredembodiments the total weight of metal of the catalyst is less than about4%. The molar ratio of platinum to (M2) may vary, for example, fromabout 20:1 to about 1:10. In various embodiments, the M1:M2 molar ratiois in the range of from about 10:1 to about 1:5. In still more preferredembodiments, the ratio of M1:M2 is in the range of about 8:1 to about1:2.

Typically, the conversion of 1,2,6-hexanetriol to HDO is conducted at atemperature in the range of about 60° C. to about 200° C. or about 120°C. to about 180° C. and a partial pressure of hydrogen in the range ofabout 200 psig to about 2000 psig or about 500 psig to about 2000 psig.

Catalytic Amination of 1,6-Hexanediol

Furthermore, the catalyst compositions of the present invention are alsouseful for the selective amination of 1,6-hexanediol (HDO) to1,6-hexamethylenediamine (HMDA). Accordingly, another process of thepresent invention is directed to the selective amination of1,6-hexanediol to 1,6-hexamethylenediamine comprising reacting the HDOwith an amine in the presence of a catalyst composition as disclosedherein. In various embodiments of this process, the catalytically activecomponent of the catalyst composition comprises ruthenium.

In some embodiments of this process, the catalytically active componentof the catalyst composition comprises ruthenium and optionally a secondmetal such as rhenium or nickel. One or more other d-block metals, oneor more rare earth metals (e.g., lanthanides), and/or one or more maingroup metals (e.g., Al) may also be present in combination withruthenium and with ruthenium and rhenium combinations. In selectembodiments, the catalytically active phase consists essentially ofruthenium and rhenium. Typically, the total weight of metal(s) is fromabout 0.1% to about 10%, from about 1% to about 6%, or from about 1% toabout 5% of the total weight of the catalyst composition.

When the catalysts of the present invention comprise ruthenium andrhenium in combination, the molar ratio of ruthenium to rhenium isimportant. A by-product of processes for converting HDO to HMDA ispentylamine. Pentylamine is an off path by-product of the conversion ofHDO to HMDA that cannot be converted to HMDA or to an intermediate whichcan, on further reaction in the presence of the catalysts of the presentinvention, be converted to HMDA. However, the presence of too muchrhenium can have an adverse effect on the yield of HMDA per unit areatime (commonly known as space time yield, or STY). Therefore, the molarratio of ruthenium:rhenium should be maintained in the range of fromabout 20:1 to about 4:1. In various embodiments, the ruthenium:rheniummolar ratio is in the range of from about 10:1 to about 4:1 or fromabout 8:1 to about 4:1. In some embodiments, the ruthenium:rhenium molarratio of from about 8:1 to about 4:1 produces HMDA in at least 25% yieldwith an HMDA/pentylamine ratio of at least 20:1, at least 25:1, or atleast 30:1.

In accordance with the present invention, HDO is converted to HMDA byreacting HDO with an amine, e.g., ammonia, in the presence of thecatalysts of the present invention. Generally, in some embodiments, theamine may be added to the reaction in the form of a gas or liquid.Typically, the molar ratio of ammonia to HDO is at least about 40:1, atleast about 30:1, or at least about 20:1. In various embodiments, it isin the range of from about 40:1 to about 5:1, from about 30:1 to about10:1. The reaction of HDO with amine in the presence of the catalystcomposition of the present invention is carried out at a temperatureless than or equal to about 200° C. In various embodiments, the catalystcomposition is contacted with HDO and amine at a temperature less thanor equal to about 100° C. In some embodiments, the catalyst is contactedwith HDO and amine at a temperature in the range of about 100° C. toabout 180° C. or about 140° C. to about 180° C.

Generally, in accordance with the present invention, the reaction isconducted at a pressure not exceeding about 1500 psig. In variousembodiments, the reaction pressure is in the range of about 200 psig toabout 1500 psig. In other embodiments, and a pressure in the range ofabout 400 psig to about 1200 psig. In certain preferred embodiments, thepressure in the range of about 400 psig to about 1000 psig. In someembodiments, the disclosed pressure ranges includes the pressure of NH₃gas and an inert gas, such as N₂. In some embodiments, the pressure ofNH₃ gas is in the range of about 50-150 psig and an inert gas, such asN₂ is in the range of about 700 psig to about 1450 psig.

In some embodiments, the catalyst is contacted with HDO and ammonia at atemperature in the range of about 100° C. to about 180° C. and apressure in the range of about 200 psig to about 1500 psig. In otherembodiments, the catalyst is contacted with HDO and ammonia at atemperature in the range of about 140° C. to about 180° C. and apressure in the range of about 400 psig to about 1200 psig. In someembodiments, the disclosed pressure ranges includes the pressure of NH₃gas and an inert gas, such as N₂. In some embodiments, the pressure ofNH₃ gas is in the range of about 50-150 psig and an inert gas, such asN₂ is in the range of about 500 psig to about 1450 psig.

The process of the present invention may be carried out in the presenceof hydrogen. Typically, in those embodiments in which the HDO and amineare reacted in the presence of hydrogen and the catalyst of the presentinvention, the hydrogen partial pressure is equal to or less than about100 psig.

The conversion of HDO to HMDA can also be conducted in the presence of asolvent. Solvents suitable for use in conjunction with the conversion ofHDO to HMDA in the presence of the catalysts of the present inventionmay include, for example, water, alcohols, esters, ethers, ketones, ormixtures thereof. In various embodiments, the preferred solvent iswater.

The chemocatalytic conversion of HDO to HMDA is likely to produce one ormore by-products such as, for example, pentylamine and hexylamine.By-products which are subsequently convertible to HMDA by furtherreaction in the presence of catalysts of the present invention areconsidered on-path by-products. Other by-products such as, for example,pentylamine and hexylamine are considered off path by-products for thereasons above discussed. In accordance with the present invention, atleast 20%, at least 30%, at least 40%, at least 50%, at least 60%, or atleast 70% of the product mixture resulting from a single pass reactionof HDO with amine (e.g., ammonia) in the presence of the catalysts ofthe present invention is HMDA.

The product mixture may be separated into one or more products by anysuitable methods known in the art. In some embodiments, the productmixture can be separated by fractional distillation under subatmosphericpressures. For example, in some embodiments, HMDA can be separated fromthe product mixture at a temperature between about 180° C. and about220° C. The HDO may be recovered from any remaining other products ofthe reaction mixture by one or more conventional methods known in theart including, for example, solvent extraction, crystallization orevaporative processes. The on-path by-products can be recycled to thereactor employed to produce the product mixture or, for example,supplied to a second reactor in which the on path by-products arefurther reacted with ammonia in the presence of the catalysts of thepresent invention to produce additional HMDA.

EMBODIMENTS

For further illustration, additional non-limiting embodiments of thepresent disclosure are set forth below.

Embodiment A1 is a shaped porous carbon product comprising:

carbon black and

a carbonized binder comprising a carbonization product of a watersoluble organic binder, wherein the shaped porous carbon product has aBET specific surface area from about 20 m²/g to about 500 m²/g or fromabout 25 m²/g to about 250 m²/g, a mean pore diameter greater than about10 nm, a specific pore volume greater than about 0.1 cm³/g, and a radialpiece crush strength greater than about 4.4 N/mm (1 lb/mm).

Embodiment A2 is the shaped porous carbon product of embodiment A1,wherein the shaped porous carbon product has a BET specific surface areafrom about 25 m²/g to about 225 m²/g, from about 25 m²/g to about 200m²/g, from about 25 m²/g to about 175 m²/g, from about 25 m²/g to about150 m²/g, from about 25 m²/g to about 125 m²/g, or from about 25 m²/g toabout 100 m²/g.

Embodiment A3 is the shaped porous carbon product of embodiment A1,wherein the shaped porous carbon product has a BET specific surface areafrom about 30 m²/g to about 225 m²/g, from about 30 m²/g to about 200m²/g, from about 30 m²/g to about 175 m²/g, from about 30 m²/g to about150 m²/g, from about 30 m²/g to about 125 m²/g, or from about 30 m²/g toabout 100 m²/g.

Embodiment A4 is the shaped porous carbon product of any one ofembodiments A1 to A3, wherein the shaped porous carbon product has amean pore diameter greater than about 12 nm or greater than about 14 nm.

Embodiment A5 is the shaped porous carbon product of any one ofembodiments A1 to A3, wherein the shaped porous carbon product has amean pore diameter from about 10 nm to about 100 nm, from about 10 nm toabout 70 nm, from 10 nm to about 50 nm, or from about 10 nm to about 25nm.

Embodiment A6 is the shaped porous carbon product of any one ofembodiments A1 to A5, wherein the shaped porous carbon product has aspecific pore volume greater than about 0.2 cm³/g or greater than about0.3 cm³/g.

Embodiment A7 is the shaped porous carbon product of any one ofembodiments A1 to A5, wherein the shaped porous carbon product has aspecific pore volume of from about 0.1 cm³/g to about 1.5 cm³/g, fromabout 0.1 cm³/g to about 0.9 cm³/g, from about 0.1 cm³/g to about 0.8cm³/g, from about 0.1 cm³/g to about 0.7 cm³/g, from about 0.1 cm³/g toabout 0.6 cm³/g, from about 0.1 cm³/g to about 0.5 cm³/g, from about 0.2cm³/g to about 1 cm³/g, from about 0.2 cm³/g to about 0.9 cm³/g, fromabout 0.2 cm³/g to about 0.8 cm³/g, from about 0.2 cm³/g to about 0.7cm³/g, from about 0.2 cm³/g to about 0.6 cm³/g, from about 0.2 cm³/g toabout 0.5 cm³/g, from about 0.3 cm³/g to about 1 cm³/g, from about 0.3cm³/g to about 0.9 cm³/g, from about 0.3 cm³/g to about 0.8 cm³/g, fromabout 0.3 cm³/g to about 0.7 cm³/g, from about 0.3 cm³/g to about 0.6cm³/g, or from about 0.3 cm³/g to about 0.5 cm³/g.

Embodiment A8 is the shaped porous carbon product of any one ofembodiments A1 to A7, wherein the shaped porous carbon product has apore volume measured on the basis of pores having a diameter from 1.7 nmto 100 nm and at least about 35%, at least about 40%, at least about45%, or at least about 50% of the pore volume is attributable to poreshaving a mean pore diameter of from about 10 nm to about 50 nm.

Embodiment A9 is the shaped porous carbon product of any one ofembodiments A1 to A7, wherein the shaped porous carbon product has apore volume measured on the basis of pores having a diameter from 1.7 nmto 100 nm and from about 35% to about 80%, from about 35% to about 75%,from about 35% to about 65%, from about 40% to about 80%, from about 40%to about 75%, from about 40% to about 70% of the pore volume isattributable to pores having a mean pore diameter of from about 10 nm toabout 50 nm.

Embodiment A10 is the shaped porous carbon product of any one ofembodiments A1 to A9, wherein the shaped porous carbon product has apore volume measured on the basis of pores having a diameter from 1.7 nmto 150 nm and at least about 35%, at least about 40%, at least about45%, or at least about 50% of the pore volume is attributable to poreshaving a mean pore diameter of from about 10 nm to about 50 nm.

Embodiment A11 is the shaped porous carbon product of any one ofembodiments A1 to A9, wherein the shaped porous carbon product has apore volume measured on the basis of pores having a diameter from 1.7 nmto 150 nm and from about 35% to about 80%, from about 35% to about 75%,from about 35% to about 65%, from about 40% to about 80%, from about 40%to about 75%, from about 40% to about 70% of the pore volume isattributable to pores having a mean pore diameter of from about 10 nm toabout 50 nm.

Embodiment A12 is the shaped porous carbon product of any one ofembodiments A1 to A11, wherein the shaped porous carbon product has apore volume measured on the basis of pores having a diameter from 1.7 nmto 200 nm and at least about 35%, at least about 40%, at least about45%, or at least about 50% of the pore volume is attributable to poreshaving a mean pore diameter of from about 10 nm to about 50 nm.

Embodiment A13 is the shaped porous carbon product of any one ofembodiments A1 to A11, wherein the shaped porous carbon product has apore volume measured on the basis of pores having a diameter from 1.7 nmto 200 nm and from about 35% to about 80%, from about 35% to about 75%,from about 35% to about 65%, from about 40% to about 80%, from about 40%to about 75%, from about 40% to about 70% of the pore volume isattributable to pores having a mean pore diameter of from about 10 nm toabout 50 nm.

Embodiment A14 is the shaped porous carbon product of any one ofembodiments A1 to A13, wherein the shaped porous carbon product has apore volume measured on the basis of pores having a diameter from 1.7 nmto 250 nm and at least about 35%, at least about 40%, at least about45%, or at least about 50% of the pore volume is attributable to poreshaving a mean pore diameter of from about 10 nm to about 50 nm.

Embodiment A15 is the shaped porous carbon product of any one ofembodiments A1 to A13, wherein the shaped porous carbon product has apore volume measured on the basis of pores having a diameter from 1.7 nmto 250 nm and from about 35% to about 80%, from about 35% to about 75%,from about 35% to about 65%, from about 40% to about 80%, from about 40%to about 75%, from about 40% to about 70% of the pore volume isattributable to pores having a mean pore diameter of from about 10 nm toabout 50 nm.

Embodiment A16 is the shaped porous carbon product of any one ofembodiments A1 to A15, wherein the shaped porous carbon product has apore volume measured on the basis of pores having a diameter from 1.7 nmto 300 nm and at least about 35%, at least about 40%, at least about45%, or at least about 50% of the pore volume is attributable to poreshaving a mean pore diameter of from about 10 nm to about 50 nm.

Embodiment A11 is the shaped porous carbon product of any one ofembodiments A1 to A15, wherein the shaped porous carbon product has apore volume measured on the basis of pores having a diameter from 1.7 nmto 300 nm and from about 35% to about 80%, from about 35% to about 75%,from about 35% to about 65%, from about 40% to about 80%, from about 40%to about 75%, from about 40% to about 70% of the pore volume isattributable to pores having a mean pore diameter of from about 10 nm toabout 50 nm.

Embodiment A18 is the shaped porous carbon product of any one ofembodiments A1 to A17, wherein the shaped porous carbon product has apore size distribution such that peaks below about 10 nm or about 5 nmare not observed.

Embodiment A19 is the shaped porous carbon product of any one ofembodiments A1 to A18, wherein the shaped porous carbon product has aradial piece crush strength greater than about 8.8 N/mm (2 lbs/mm) orgreater than about 13.3 N/mm (3 lbs/mm).

Embodiment A20 is the shaped porous carbon product of any one ofembodiments A1 to A18, wherein the shaped porous carbon product has aradial piece crush strength from about 4.4 N/mm (1 lb/mm) to about 88N/mm (20 lbs/mm), from about 4.4 N/mm (1 lb/mm) to about 66 N/mm (15lbs/mm), or from about 8.8 N/mm (2 lb/mm) to about 44 N/mm (10 lbs/mm).

Embodiment A21 is the shaped porous carbon product of any one ofembodiments A1 to A20, wherein the shaped porous carbon product has amechanical piece crush strength greater than about 22 N (5 lbs), greaterthan about 36 N (8 lbs), or greater than about 44 N (10 lbs).

Embodiment A22 is the shaped porous carbon product of any one ofembodiments A1 to A20, wherein the shaped porous carbon product has amechanical piece crush strength from about 22 N (5 lbs) to about 88 N(20 lbs), from about 22 N (5 lbs) to about 66 N (15 lbs), or from about33 N (7.5 lbs) to about 66 N (15 lbs).

Embodiment A23 is the shaped porous carbon product of any one ofembodiments A1 to A22, wherein the shaped porous carbon product has amean diameter of at least about 50 μm, at least about 500 μm, at leastabout 1,000 μm, or at least about 10,000 μm.

Embodiment A24 is the shaped porous carbon product of any one ofembodiments A1 to A23, wherein the carbon black content of the shapedporous carbon product is at least about 35 wt. %, at least about 40 wt.%, at least about 45 wt. %, at least about 50 wt. %, at least about 55wt. %, at least about 60 wt. %, at least about 65 wt. %, or at leastabout 70 wt. %.

Embodiment A25 is the shaped porous carbon product of any one ofembodiments A1 to A23, wherein the carbon black content of the shapedporous carbon product is from about 35 wt. % to about 80 wt. %, fromabout 35 wt. % to about 75 wt. %, from about 40 wt. % to about 80 wt. %,or from about 40 wt. % to about 75 wt. %.

Embodiment A26 is the shaped porous carbon product of any one ofembodiments A1 to A25, wherein the carbon black comprises conductivecarbon black.

Embodiment A27 is the shaped porous carbon product of any one ofembodiments A1 to A26, wherein the carbon black comprises nonconductivecarbon black.

Embodiment A28 is the shaped porous carbon product of embodiment A27,wherein the shaped porous carbon product does not exhibit a conductivitythat is suitable for a conductive electrode.

Embodiment A29 is the shaped porous carbon product of embodiment A27 orA28, wherein the shaped porous carbon product comprises nonconductivecarbon black and less than about 50%, less than about 40%, less thanabout 30%, less than about 20%, less than about 10%, less than about 5%,or less than about 1% conductive carbon black based on the total weightof the carbon black in the shaped porous carbon product.

Embodiment A30 is the shaped porous carbon product of any one ofembodiments A1 to A25, wherein the shaped porous carbon productcomprises carbon black consisting essentially of nonconductive carbonblack.

Embodiment A31 is the shaped porous carbon product of any one ofembodiments A1 to A25, wherein the shaped porous carbon productcomprises carbon black consisting of nonconductive carbon black.

Embodiment A32 is the shaped porous carbon product of any one ofembodiments A1 to A31, wherein the shaped porous carbon product has acarbonized binder content from about 10 wt. % to about 50 wt. %, fromabout 20 wt. % to about 50 wt. %, from about 25 wt. % to about 40 wt. %,or from about 25 wt. % to about 35 wt. %.

Embodiment A33 is the shaped porous carbon product of any one ofembodiments A1 to A32, wherein the water soluble organic bindercomprises a carbohydrate or derivative thereof.

Embodiment A34 is the shaped porous carbon product of embodiment A33,wherein derivatives of carbohydrates are selected from the groupconsisting of alginic acid, pectin, aldonic acids, aldaric acids, uronicacids, sugar alcohols, and salts, oligomers, and polymers thereof.

Embodiment A35 is the shaped porous carbon product of any one ofembodiments A1 to A34, wherein the water soluble organic bindercomprises a monosaccharide selected from the group consisting of aglucose, a fructose, hydrate thereof, syrup thereof, and combinationsthereof.

Embodiment A36 is the shaped porous carbon product of any one ofembodiments A1 to A35, wherein the water soluble organic bindercomprises a saccharide selected from the group consisting of maltose,sucrose, syrups thereof, soluble starches, soluble gums, andcombinations thereof.

Embodiment A37 is the shaped porous carbon product of any one ofembodiments A1 to A36, wherein the water soluble organic bindercomprises a cellulosic compound.

Embodiment A38 is the shaped porous carbon product of embodiment A37,wherein the cellulosic compound comprises hydroxyethylcellulose,hydroxypropylcellulose, hydroxyethylmethylcellulose,hydroxypropylmethylcellulose, or carboxymethylcellulose.

Embodiment A39 is the shaped porous carbon product of embodiment A37 orA38, wherein the cellulosic compound comprises alginic acid, pectin, ora salt thereof.

Embodiment A40 is the shaped porous carbon product of any one ofembodiments A1 to A39, wherein the water soluble organic bindercomprises a water soluble polymer or copolymer.

Embodiment A41 is the shaped porous carbon product of embodiment A40,wherein the water soluble polymer or copolymer is selected from thegroup consisting of polyacrylic acid, polyvinyl alcohols, polyvinylacetates, polyacrylates and copolymers derived therefrom.

Embodiment A42 is the shaped porous carbon product of any one ofembodiments A1 to A41, wherein the water soluble organic binder isselected from the group consisting of water soluble celluloses; watersoluble alcohols; water soluble acetals; water soluble acids; polyvinylacrylic acids; and salts, esters, oligomers, or polymers of any ofthese.

Embodiment A43 is the shaped porous carbon product of any one ofembodiments A1 to A42, wherein the water soluble organic bindercomprises a saccharide in combination with one or more water solublecelluloses; water soluble alcohols; water soluble acetals; water solubleacids; polyvinyl acrylic acids; or salts, esters, oligomers, or polymersof any of these.

Embodiment A44 is the shaped porous carbon product of embodiment A43,wherein the saccharide comprises a monosaccharide.

Embodiment A45 is the shaped porous carbon product of embodiment A44,wherein the water soluble cellulose comprises hydroxyethylcellulose ormethylcellulose and the monosaccharide comprises a glucose, fructose orhydrate thereof.

Embodiment A46 is the shaped porous carbon product of embodiment A45,wherein the water soluble cellulose comprises hydroxyethylcellulose andthe monosaccharide comprises a glucose or hydrate thereof.

Embodiment A47 is the shaped porous carbon product of any of embodimentsA42 to A46, wherein the water soluble alcohol is selected from the groupconsisting of sorbitol, mannitol, xylitol and a polyvinyl alcohol.

Embodiment A48 is the shaped porous carbon product of any of embodimentsA42 to A46, wherein the water soluble acid is selected from the groupconsisting of stearic acid, pectin, alginic acid, polyacrylic acid, andsalts thereof.

Embodiment A49 is the shaped porous carbon product of any of embodimentsA1 to A48, wherein the sulfur content of the shaped porous carbonproduct is no greater than about 1 wt. % or no greater than about 0.1wt. %.

Embodiment B1 is a shaped porous carbon product comprising a carbonagglomerate, wherein the shaped porous carbon product has a meandiameter of at least about 50 μm, a BET specific surface area from about20 m²/g to about 500 m²/g, a mean pore diameter greater than about 10nm, a specific pore volume greater than about 0.1 cm³/g, and a radialpiece crush strength greater than about 4.4 N/mm (1 lb/mm).

Embodiment B2 is the shaped porous carbon product of embodiment B1,wherein the shaped porous carbon product has a BET specific surface areafrom about 25 m²/g to about 250 m²/g, from about 25 m²/g to about 225m²/g, from about 25 m²/g to about 200 m²/g, from about 25 m²/g to about175 m²/g, from about 25 m²/g to about 150 m²/g, from about 25 m²/g toabout 125 m²/g, or from about 25 m²/g to about 100 m²/g.

Embodiment B3 is the shaped porous carbon product of embodiment B1,wherein the shaped porous carbon product has a BET specific surface areafrom about 30 m²/g to about 225 m²/g, from about 30 m²/g to about 200m²/g, from about 30 m²/g to about 175 m²/g, from about 30 m²/g to about150 m²/g, from about 30 m²/g to about 125 m²/g, or from about 30 m²/g toabout 100 m²/g.

Embodiment B4 is the shaped porous carbon product of any one ofembodiments B1 to B3, wherein the shaped porous carbon product has amean pore diameter greater than about 12 nm or greater than about 14 nm.

Embodiment B5 is the shaped porous carbon product of any one ofembodiments B1 to B3, wherein the shaped porous carbon product has amean pore diameter from about 10 nm to about 100 nm, from about 10 nm toabout 70 nm, from 10 nm to about 50 nm, or from about 10 nm to about 25nm.

Embodiment B6 is the shaped porous carbon product of any one ofembodiments B1 to B5, wherein the shaped porous carbon product has aspecific pore volume greater than about 0.2 cm³/g or greater than about0.3 cm³/g.

Embodiment B7 is the shaped porous carbon product of any one ofembodiments B1 to B5, wherein the shaped porous carbon product has aspecific pore volume of from about 0.1 cm³/g to about 1.5 cm³/g, fromabout 0.1 cm³/g to about 0.9 cm³/g, from about 0.1 cm³/g to about 0.8cm³/g, from about 0.1 cm³/g to about 0.7 cm³/g, from about 0.1 cm³/g toabout 0.6 cm³/g, from about 0.1 cm³/g to about 0.5 cm³/g, from about 0.2cm³/g to about 1 cm³/g, from about 0.2 cm³/g to about 0.9 cm³/g, fromabout 0.2 cm³/g to about 0.8 cm³/g, from about 0.2 cm³/g to about 0.7cm³/g, from about 0.2 cm³/g to about 0.6 cm³/g, from about 0.2 cm³/g toabout 0.5 cm³/g, from about 0.3 cm³/g to about 1 cm³/g, from about 0.3cm³/g to about 0.9 cm³/g, from about 0.3 cm³/g to about 0.8 cm³/g, fromabout 0.3 cm³/g to about 0.7 cm³/g, from about 0.3 cm³/g to about 0.6cm³/g, or from about 0.3 cm³/g to about 0.5 cm³/g.

Embodiment B8 is the shaped porous carbon product of any one ofembodiments B1 to B7, wherein the shaped porous carbon product has apore volume measured on the basis of pores having a diameter from 1.7 nmto 100 nm and at least about 35%, at least about 40%, at least about45%, or at least about 50% of the pore volume is attributable to poreshaving a mean pore diameter of from about 10 nm to about 50 nm.

Embodiment B9 is the shaped porous carbon product of any one ofembodiments B1 to B7, wherein the shaped porous carbon product has apore volume measured on the basis of pores having a diameter from 1.7 nmto 100 nm and from about 35% to about 80%, from about 35% to about 75%,from about 35% to about 65%, from about 40% to about 80%, from about 40%to about 75%, from about 40% to about 70% of the pore volume isattributable to pores having a mean pore diameter of from about 10 nm toabout 50 nm.

Embodiment B10 is the shaped porous carbon product of any one ofembodiments B1 to B9, wherein the shaped porous carbon product has apore volume measured on the basis of pores having a diameter from 1.7 nmto 150 nm and at least about 35%, at least about 40%, at least about45%, or at least about 50% of the pore volume is attributable to poreshaving a mean pore diameter of from about 10 nm to about 50 nm.

Embodiment B11 is the shaped porous carbon product of any one ofembodiments B1 to B9, wherein the shaped porous carbon product has apore volume measured on the basis of pores having a diameter from 1.7 nmto 150 nm and from about 35% to about 80%, from about 35% to about 75%,from about 35% to about 65%, from about 40% to about 80%, from about 40%to about 75%, from about 40% to about 70% of the pore volume isattributable to pores having a mean pore diameter of from about 10 nm toabout 50 nm.

Embodiment B12 is the shaped porous carbon product of any one ofembodiments B1 to B11, wherein the shaped porous carbon product has apore volume measured on the basis of pores having a diameter from 1.7 nmto 200 nm and at least about 35%, at least about 40%, at least about45%, or at least about 50% of the pore volume is attributable to poreshaving a mean pore diameter of from about 10 nm to about 50 nm.

Embodiment B13 is the shaped porous carbon product of any one ofembodiments B1 to B11, wherein the shaped porous carbon product has apore volume measured on the basis of pores having a diameter from 1.7 nmto 200 nm and from about 35% to about 80%, from about 35% to about 75%,from about 35% to about 65%, from about 40% to about 80%, from about 40%to about 75%, from about 40% to about 70% of the pore volume isattributable to pores having a mean pore diameter of from about 10 nm toabout 50 nm.

Embodiment B14 is the shaped porous carbon product of any one ofembodiments B1 to B13, wherein the shaped porous carbon product has apore volume measured on the basis of pores having a diameter from 1.7 nmto 250 nm and at least about 35%, at least about 40%, at least about45%, or at least about 50% of the pore volume is attributable to poreshaving a mean pore diameter of from about 10 nm to about 50 nm.

Embodiment B15 is the shaped porous carbon product of any one ofembodiments B1 to B13, wherein the shaped porous carbon product has apore volume measured on the basis of pores having a diameter from 1.7 nmto 250 nm and from about 35% to about 80%, from about 35% to about 75%,from about 35% to about 65%, from about 40% to about 80%, from about 40%to about 75%, from about 40% to about 70% of the pore volume isattributable to pores having a mean pore diameter of from about 10 nm toabout 50 nm.

Embodiment B16 is the shaped porous carbon product of any one ofembodiments B1 to B15, wherein the shaped porous carbon product has apore volume measured on the basis of pores having a diameter from 1.7 nmto 300 nm and at least about 35%, at least about 40%, at least about45%, or at least about 50% of the pore volume is attributable to poreshaving a mean pore diameter of from about 10 nm to about 50 nm.

Embodiment B17 is the shaped porous carbon product of any one ofembodiments B1 to B15, wherein the shaped porous carbon product has apore volume measured on the basis of pores having a diameter from 1.7 nmto 300 nm and from about 35% to about 80%, from about 35% to about 75%,from about 35% to about 65%, from about 40% to about 80%, from about 40%to about 75%, from about 40% to about 70% of the pore volume isattributable to pores having a mean pore diameter of from about 10 nm toabout 50 nm.

Embodiment B18 is the shaped porous carbon product of any one ofembodiments B1 to B17, wherein the shaped porous carbon product has apore size distribution such that peaks below about 10 nm or about 5 nmare not observed.

Embodiment B19 is the shaped porous carbon product of any one ofembodiments B1 to B18, wherein the shaped porous carbon product has aradial piece crush strength greater than about 8.8 N/mm (2 lbs/mm) orgreater than about 13.3 N/mm (3 lbs/mm).

Embodiment B20 is the shaped porous carbon product of any one ofembodiments B1 to B18, wherein the shaped porous carbon product has aradial piece crush strength from about 4.4 N/mm (1 lb/mm) to about 88N/mm (20 lbs/mm), from about 4.4 N/mm (1 lb/mm) to about 66 N/mm (15lbs/mm), or from about 8.8 N/mm (2 lb/mm) to about 44 N/mm (10 lbs/mm).

Embodiment B21 is the shaped porous carbon product of any one ofembodiments B1 to B20, wherein the shaped porous carbon product has amechanical piece crush strength greater than about 22 N (5 lbs), greaterthan about 36 N (8 lbs), or greater than about 44 N (10 lbs).

Embodiment B22 is the shaped porous carbon product of any one ofembodiments B1 to B20, wherein the shaped porous carbon product has amechanical piece crush strength from about 22 N (5 lbs) to about 88 N(20 lbs), from about 22 N (5 lbs) to about 66 N (15 lbs), or from about33 N (7.5 lbs) to about 66 N (15 lbs).

Embodiment B23 is the shaped porous carbon product of any one ofembodiments B1 to B22, wherein the shaped porous carbon product has amean diameter of at least about 500 μm, at least about 1,000 μm, or atleast about 10,000 μm.

Embodiment B24 is the shaped porous carbon product of any one ofembodiments B1 to B23, wherein the carbon agglomerate comprises carbonblack.

Embodiment B25 is the shaped porous carbon product of embodiment B24,wherein the carbon black content of the shaped porous carbon product isat least about 35 wt. %, at least about 40 wt. %, at least about 45 wt.%, at least about 50 wt. %, at least about 55 wt. %, at least about 60wt. %, at least about 65 wt. %, or at least about 70 wt. %.

Embodiment B26 is the shaped porous carbon product of embodiment B25,wherein the carbon black content of the shaped porous carbon product isfrom about 35 wt. % to about 80 wt. %, from about 35 wt. % to about 75wt. %, from about 40 wt. % to about 80 wt. %, or from about 40 wt. % toabout 75 wt. %.

Embodiment B27 is the shaped porous carbon product of any one ofembodiments B24 to B26, wherein the carbon black comprises conductivecarbon black.

Embodiment B28 is the shaped porous carbon product of any one ofembodiments B24 to B27, wherein the carbon black comprises nonconductivecarbon black.

Embodiment B29 is the shaped porous carbon product of embodiment B28,wherein the shaped porous carbon product does not exhibit a conductivitythat is suitable for a conductive electrode.

Embodiment B30 is the shaped porous carbon product of embodiment B28 orB29, wherein the shaped porous carbon product comprises nonconductivecarbon black and less than about 50%, less than about 40%, less thanabout 30%, less than about 20%, less than about 10%, less than about 5%,or less than about 1% conductive carbon black based on the total weightof the carbon black in shaped porous carbon product.

Embodiment B31 is the shaped porous carbon product of any one ofembodiments B24 to B26, wherein the shaped porous carbon productcomprises carbon black consisting essentially of nonconductive carbonblack.

Embodiment B32 is the shaped porous carbon product of any one ofembodiments B24 to B26, wherein the shaped porous carbon productcomprises carbon black consisting of nonconductive carbon black.

Embodiment B33 is the shaped porous carbon product of any of embodimentsB1 to B32, wherein the sulfur content of the shaped porous carbonproduct is no greater than about 1 wt. % or no greater than about 0.1wt. %.

Embodiment C1 is a catalyst composition comprising the shaped porouscarbon product of any one of embodiments A1 to A49 or B1 to B33 as acatalyst support and a catalytically active component at a surface ofthe support.

Embodiment C2 is the catalyst composition of embodiment C1, wherein thecatalytically active component comprises a metal.

Embodiment C3 is the catalyst composition of embodiment C2, wherein themetal comprises at least one d-block metal.

Embodiment C4 is the catalyst composition of embodiment C2 or C3,wherein the metal comprises at least one metal selected from groups V,VI, VII, VIII, IX, X, XI, XII, and XIII.

Embodiment C5 is the catalyst composition of any one of embodiments C2to C4, wherein the metal is selected from the group consisting ofcobalt, nickel, copper, zinc, iron, ruthenium, rhodium, rhenium,palladium, silver, osmium, iridium, platinum, gold, and combinationsthereof.

Embodiment D1 is a catalyst composition comprising a shaped porouscarbon support and a catalytically active component comprising platinumand gold at a surface of the support.

Embodiment D2 is the catalyst composition of embodiment D1, wherein theshaped porous carbon support comprises the shaped porous carbon productof any one of embodiments A1 to A49 or B1 to B33.

Embodiment D3 is the catalyst composition of embodiment D1 of D2,wherein the total metal loading of the catalyst composition is about 10wt. % or less, from about 1 wt. % to about 8 wt. %, from about 1 wt. %to about 5 wt. %, or from about 2 wt. % to about 4 wt. %.

Embodiment D4 is the catalyst composition of any one of embodiments D1to D3, wherein the catalytically active component is present in a shelllayer at external surfaces of the shaped porous carbon support.

Embodiment D5 is the catalyst composition of any one of embodiments D1to D4, wherein the shell thickness is from about 10 μm to about 400 μm,or from about 50 μm to about 150 μm.

Embodiment D6 is the catalyst composition of any one of embodiments D1to D5, wherein the molar ratio of platinum to gold is from about 100:1to about 1:4, from about 10:1 to about 1:2, from about 3:1 to about 1:2,from about 3:1 to about 1:2, or from about 2:1 to about 1:2.

Embodiment D7 is the catalyst composition of any one of embodiments D1to D6, wherein the catalytically active component comprises particlescomprising platinum having a particle size in the range of from about 1nm to about 50 nm, from about 1 nm to about 20 nm, or from about 1 nm toabout 10 nm.

Embodiment D8 is the catalyst composition of any one of embodiments D1to D7, wherein the catalytically active component comprises particlescomprising gold having a particle size in the range of about 1 to about20 nanometers or about 1 nm to about 10 nm.

Embodiment D9 is the catalyst composition of any one of embodiments D1to D8, wherein the catalytically active component comprises particlescomprising gold-platinum alloy.

Embodiment D10 is the catalyst composition of any one of embodiments D1to D9, wherein at least about 1 wt. %, at least about 5 wt. %, at leastabout 10 wt. %, at least about 15 wt. %, or at least about 20 wt. % ofthe total platinum content of the catalyst composition is present asparticles consisting essentially of platinum (0).

Embodiment E1 is a catalyst composition comprising a shaped porouscarbon support and a catalytically active component comprising platinumand rhodium at a surface of the support.

Embodiment E2 is the catalyst composition of embodiment E1, wherein theshaped porous carbon support comprises the shaped porous carbon productof any one of embodiments A1 to A49 or B1 to B33.

Embodiment E3 is the catalyst composition of embodiment E1 or E2,wherein the total metal loading of the catalyst composition is fromabout 0.1% to about 10%, or from 0.2% to about 10%, from about 0.2% toabout 8%, from about 0.2% to about 5%, or less than about 4% of thetotal weight of the catalyst.

Embodiment E4 is the catalyst composition of any one of embodiments E1to E3, wherein the catalytically active component is present in a shelllayer at external surfaces of the shaped porous carbon support.

Embodiment E5 is the catalyst composition of any one of embodiments E1to E4, wherein the shell thickness is from about 10 μm to about 400 μm,or from about 50 μm to about 150 μm.

Embodiment E6 is the catalyst composition of any one of embodiments E1to E5, wherein the molar ratio of platinum to rhodium of the catalystcomposition is in the range of from about 3:1 to about 1:2 or from about3:1 to about 1:1.

Embodiment F1 is a method of preparing a catalyst composition as definedin any one of embodiments C1 to C5, D1 to D10, or E1 to E6 comprisingdepositing a catalytically active component on the shaped porous carbonproduct of any one of embodiments A1 to A49 or B1 to B33.

Embodiment G1 is a process for the catalytic conversion of a reactantcomprising contacting a liquid medium comprising the reactant with acatalyst composition of any one of embodiments C1 to C5, D1 to D10, orE1 to E6.

Embodiment G2 is the process of embodiment G1, wherein the catalystcomposition is stable to the continuous flow of the liquid medium andreaction conditions for at least about 500 hours without substantialloss in activity.

Embodiment H1 is a process for the selective oxidation of an aldose toan aldaric acid comprising reacting the aldose with oxygen in thepresence of a catalyst composition of any one of embodiments C1 to C5 orD1 to D10 to form the aldaric acid.

Embodiment H2 is the process of embodiment H1, wherein the aldose isselected from the group consisting of pentoses and hexoses.

Embodiment H3 is the process of embodiment H1 or H2, wherein the aldaricacid is selected from the group consisting of xylaric acid and glucaricacid.

Embodiment H4 is the process of any one of embodiments H1 to H3, whereinthe catalytically active component of the catalyst composition comprisesat least platinum.

Embodiment H5 is the process of any one of embodiments H1 to H4, whereinthe catalytically active component of the catalyst composition comprisesplatinum and gold.

Embodiment H6 is the process of any one of embodiments H1 to H5, whereinthe aldaric acid comprises glucaric acid and the glucaric acid yield isat least about 30%, at least about 35%, at least about 40%, at leastabout, 45%, or at least about 50%.

Embodiment H7 is the process of any one of embodiments H1 to H5, whereinthe aldaric acid comprises glucaric acid and the glucaric acid yield isfrom about 35% to about 65%, from about 40% to about 65%, or from about45% to about 65%.

Embodiment H8 is the process of any one of embodiments H1 to H7, whereinthe aldaric acid comprises glucaric acid and the glucaric acidselectivity is at least about 70%, at least about 75%, or at least about80%.

Embodiment H9 is the process of any one of embodiments H1 to H8, whereinthe aldose comprises glucose and the catalytically active componentcomprises platinum and the mass ratio of glucose to platinum is fromabout 10:1 to about 1000:1, from about 10:1 to about 500:1, from about10:1 to about 200:1, or from about 10:1 to about 100:1.

Embodiment I1 is a process for the selective hydrodeoxygenation ofaldaric acid or salt, ester, or lactone thereof to a dicarboxylic acidcomprising:

reacting the aldaric acid or salt, ester, or lactone thereof withhydrogen in the presence of a halogen-containing compound and a catalystcomposition of any one of embodiments C1 to C5 or E1 to E6 to form thedicarboxylic acid.

Embodiment 12 is the process of embodiment I1, wherein the aldaric acidor salt, ester, or lactone thereof comprises glucaric acid or salt,ester, or lactone thereof.

Embodiment 13 is the process of embodiment I1 or 12, wherein thedicarboxylic acid comprises adipic acid.

Embodiment 14 is the process of any one of embodiments I1 to 13, whereinthe catalytically active component of the catalyst composition comprisesat least one noble metal.

Embodiment K1 is a method of preparing a reactor vessel for a liquidphase catalytic reaction comprising charging the reactor vessel with acatalyst composition of any one of embodiments C1 to C5, D1 to D10, orE1 to E6.

Embodiment L1 is a method of preparing a shaped porous carbon productcomprising:

mixing carbon black particles with a solution comprising a water solubleorganic binder compound to produce a slurry;

forming the slurry to produce a shaped carbon black composite; and

heating the shaped carbon black composite to carbonize the binder to awater insoluble state to produce the shaped porous carbon product.

Embodiment L2 is the method of embodiment L1, wherein the weight ratioof binder to carbon black in the slurry is at least about 1:4, at leastabout 1:3, at least about 1:2, or at least about 1:1.

Embodiment L3 is the method of embodiment L1, wherein the weight ratioof binder to carbon black in the slurry is from about 1:4 to about 3:1,from about 1:4 to about 1:1, from about 1:3 to about 2:1, from about 1:3to about 1:1, or about 1:1.

Embodiment L4 is the method of any one of embodiments L1 to L3, whereinthe carbon black content of the slurry is at least about 35 wt. %, atleast about 40 wt. %, at least about 45 wt. %, at least about 50 wt. %,at least about 55 wt. %, at least about 60 wt. %, at least about 65 wt.%, or at least about 70 wt. % on a dry weight basis.

Embodiment L5 is the method of any one of embodiments L1 to L3, whereinthe carbon black content of the slurry is from about 35 wt. % to about80 wt. %, from about 35 wt. % to about 75 wt. %, from about 40 wt. % toabout 80 wt. %, or from about 40 wt. % to about 75 wt. % on a dry weightbasis.

Embodiment L6 is the method of any one of embodiments L1 to L5, whereinthe binder content of the slurry is at least about 10 wt. %, at leastabout 20 wt. %, at least about 25 wt. %, at least about 30 wt. %, atleast about 35 wt. %, at least about 40 wt. %, or at least 45 wt. %binder on a dry weight basis.

Embodiment L7 is the method of any one of embodiments L1 to L5, whereinthe binder content of the slurry is from about 10 wt. % to about 50 wt.%, from about 10 wt. % to about 45 wt. %, from about 15 wt. % to about50 wt. %, from about 20 wt. % to about 50 wt. %, or from about 20 wt. %to about 45 wt. % on a dry weight basis.

Embodiment L8 is the method of any one of embodiments L1 to L7, whereinheating the carbon black composite to carbonize the binder is conductedin an inert, oxidative, or reductive atmosphere.

Embodiment L9 is the method of embodiment L8, wherein the atmosphere isan inert nitrogen atmosphere.

Embodiment L10 is the method of any one of embodiments L1 to L9, whereinheating the carbon black composite to carbonize the binder is conductedat a temperature of from about 250° C. to about 1,000° C., from about300° C. to about 900° C., from about 300° C. to about 800° C., fromabout 350° C. to about 800° C., from about 350° C. to about 700° C., orfrom about 400° C. to about 800° C.

Embodiment L11 is the method of any one of embodiments L1 to L10,further comprising mixing a porogen with the carbon black and binder.

Embodiment L12 is the method of any one of embodiments L1 to L11,further comprising drying the shaped carbon black composite afterforming.

Embodiment L13 is the method of embodiment L12, wherein drying theshaped carbon black composite comprises heating at a temperature of fromabout 20° C. to about 150° C., from about 40° C. to about 120° C., orfrom about 60° C. to about 120° C.

Embodiment L14 is the method of embodiment L12, wherein drying theshaped carbon black composite comprises a method selected from the groupconsisting of vacuum drying, freeze drying, and desiccation.

Embodiment L15 is the method of any one of embodiments L1 to L14,further comprising washing the shaped porous carbon product.

Embodiment L16 is the method of any one of embodiments L1 to L15,wherein the shaped carbon black composite is formed by extruding theslurry.

Embodiment L17 is the method of any one of embodiments L1 to L16,wherein the slurry is formed under a pressure of at least about 100 kPa(1 bar), or between about 100 kPa (1 bar) to about 10,000 kPa (100 bar),between 500 kPa (5 bar) and 5,000 kPa (50 bar), or between 1,000 kPa (10bar) and 3,000 kPa (30 bar).

Embodiment L18 is the method of any one of embodiments L1 to L15,wherein the shaped carbon black composite is formed by drip casting theslurry.

Embodiment L19 is the method of embodiment L18, wherein drip castingcomprises:

dispensing droplets of the slurry into a casting bath to form the shapedcarbon black composite; and

separating the shaped carbon black composite from the casting bath.

Embodiment L20 is the method of embodiment L19, wherein the casting bathcomprises an ionic salt.

Embodiment L21 is the method of embodiment L20, wherein the ionic saltis a calcium salt.

Embodiment L22 is the method of embodiment L21, wherein the bindercomprises an alginate.

Embodiment L23 is the method of embodiment L19, wherein the casting bathcomprises an oil.

Embodiment L24 is the method of embodiment L19, wherein the casting bathis a freeze drying bath.

Embodiment L25 is the method of any one of embodiments L1 to L24,wherein the shaped porous carbon product has a BET specific surface areafrom about 20 m²/g to about 500 m²/g or from about 25 m²/g to about 250m²/g, from about 25 m²/g to about 250 m²/g, from about 25 m²/g to about225 m²/g, from about 25 m²/g to about 200 m²/g, from about 25 m²/g toabout 175 m²/g, from about 25 m²/g to about 150 m²/g, from about 25 m²/gto about 125 m²/g, or from about 25 m²/g to about 100 m²/g.

Embodiment L26 is the method of any one of embodiments L1 to L24,wherein the shaped porous carbon product has a BET specific surface areafrom about 30 m²/g to about 225 m²/g, from about 30 m²/g to about 200m²/g, from about 30 m²/g to about 175 m²/g, from about 30 m²/g to about150 m²/g, from about 30 m²/g to about 125 m²/g, or from about 30 m²/g toabout 100 m²/g.

Embodiment L27 is the method of any one of embodiments L1 to L26,wherein the shaped porous carbon product has a mean pore diametergreater than about 10 nm, greater than about 12 nm, or greater thanabout 14 nm.

Embodiment L28 is the method of any one of embodiments L1 to L26,wherein the shaped porous carbon product has a mean pore diameter fromabout 10 nm to about 100 nm, from about 10 nm to about 70 nm, from 10 nmto about 50 nm, or from about 10 nm to about 25 nm.

Embodiment L29 is the method of any one of embodiments L1 to L28,wherein the shaped porous carbon product has a specific pore volumegreater than about 0.1 cm³/g, greater than about 0.2 cm³/g, or greaterthan about 0.3 cm³/g.

Embodiment L30 is the method of any one of embodiments L1 to L28,wherein the shaped porous carbon product has a specific pore volume offrom about 0.1 cm³/g to about 1.5 cm³/g, from about 0.1 cm³/g to about0.9 cm³/g, from about 0.1 cm³/g to about 0.8 cm³/g, from about 0.1 cm³/gto about 0.7 cm³/g, from about 0.1 cm³/g to about 0.6 cm³/g, from about0.1 cm³/g to about 0.5 cm³/g, from about 0.2 cm³/g to about 1 cm³/g,from about 0.2 cm³/g to about 0.9 cm³/g, from about 0.2 cm³/g to about0.8 cm³/g, from about 0.2 cm³/g to about 0.7 cm³/g, from about 0.2 cm³/gto about 0.6 cm³/g, from about 0.2 cm³/g to about 0.5 cm³/g, from about0.3 cm³/g to about 1 cm³/g, from about 0.3 cm³/g to about 0.9 cm³/g,from about 0.3 cm³/g to about 0.8 cm³/g, from about 0.3 cm³/g to about0.7 cm³/g, from about 0.3 cm³/g to about 0.6 cm³/g, or from about 0.3cm³/g to about 0.5 cm³/g.

Embodiment L31 is the method of any one of embodiments L1 to L30,wherein the shaped porous carbon product has a pore volume measured onthe basis of pores having a diameter from 1.7 nm to 100 nm and at leastabout 35%, at least about 40%, at least about 45%, or at least about 50%of the pore volume is attributable to pores having a mean pore diameterof from about 10 nm to about 50 nm.

Embodiment L32 is the method of any one of embodiments L1 to L30,wherein the shaped porous carbon product has a pore volume measured onthe basis of pores having a diameter from 1.7 nm to 100 nm and fromabout 35% to about 80%, from about 35% to about 75%, from about 35% toabout 65%, from about 40% to about 80%, from about 40% to about 75%,from about 40% to about 70% of the pore volume is attributable to poreshaving a mean pore diameter of from about 10 nm to about 50 nm.

Embodiment L33 is the method of any one of embodiments L1 to L32,wherein the shaped porous carbon product has a pore volume measured onthe basis of pores having a diameter from 1.7 nm to 150 nm and at leastabout 35%, at least about 40%, at least about 45%, or at least about 50%of the pore volume is attributable to pores having a mean pore diameterof from about 10 nm to about 50 nm.

Embodiment L34 is the method of any one of embodiments L1 to L32,wherein the shaped porous carbon product has a pore volume measured onthe basis of pores having a diameter from 1.7 nm to 150 nm and fromabout 35% to about 80%, from about 35% to about 75%, from about 35% toabout 65%, from about 40% to about 80%, from about 40% to about 75%,from about 40% to about 70% of the pore volume is attributable to poreshaving a mean pore diameter of from about 10 nm to about 50 nm.

Embodiment L35 is the method of any one of embodiments L1 to L34,wherein the shaped porous carbon product has a pore volume measured onthe basis of pores having a diameter from 1.7 nm to 200 nm and at leastabout 35%, at least about 40%, at least about 45%, or at least about 50%of the pore volume is attributable to pores having a mean pore diameterof from about 10 nm to about 50 nm.

Embodiment L36 is the method of any one of embodiments L1 to L34,wherein the shaped porous carbon product has a pore volume measured onthe basis of pores having a diameter from 1.7 nm to 200 nm and fromabout 35% to about 80%, from about 35% to about 75%, from about 35% toabout 65%, from about 40% to about 80%, from about 40% to about 75%,from about 40% to about 70% of the pore volume is attributable to poreshaving a mean pore diameter of from about 10 nm to about 50 nm.

Embodiment L37 is the method of any one of embodiments L1 to L36,wherein the shaped porous carbon product has a pore volume measured onthe basis of pores having a diameter from 1.7 nm to 250 nm and at leastabout 35%, at least about 40%, at least about 45%, or at least about 50%of the pore volume is attributable to pores having a mean pore diameterof from about 10 nm to about 50 nm.

Embodiment L38 is the method of any one of embodiments L1 to L36,wherein the shaped porous carbon product has a pore volume measured onthe basis of pores having a diameter from 1.7 nm to 250 nm and fromabout 35% to about 80%, from about 35% to about 75%, from about 35% toabout 65%, from about 40% to about 80%, from about 40% to about 75%,from about 40% to about 70% of the pore volume is attributable to poreshaving a mean pore diameter of from about 10 nm to about 50 nm.

Embodiment L39 is the method of any one of embodiments L1 to L38,wherein the shaped porous carbon product has a pore volume measured onthe basis of pores having a diameter from 1.7 nm to 300 nm and at leastabout 35%, at least about 40%, at least about 45%, or at least about 50%of the pore volume is attributable to pores having a mean pore diameterof from about 10 nm to about 50 nm.

Embodiment L40 is the method of any one of embodiments L1 to L38,wherein the shaped porous carbon product has a pore volume measured onthe basis of pores having a diameter from 1.7 nm to 300 nm and fromabout 35% to about 80%, from about 35% to about 75%, from about 35% toabout 65%, from about 40% to about 80%, from about 40% to about 75%,from about 40% to about 70% of the pore volume is attributable to poreshaving a mean pore diameter of from about 10 nm to about 50 nm.

Embodiment L41 is the method of any one of embodiments L1 to L40,wherein the shaped porous carbon product has a pore size distributionsuch that peaks below about 10 nm or about 5 nm are not observed.

Embodiment L42 is the method of any one of embodiments L1 to L41,wherein the shaped porous carbon product has a radial piece crushstrength greater than about 4.4 N/mm (1 lb/mm), greater than about 8.8N/mm (2 lbs/mm), or greater than about 13.3 N/mm (3 lbs/mm).

Embodiment L43 is the method of any one of embodiments L1 to L41,wherein the shaped porous carbon product has a radial piece crushstrength from about 4.4 N/mm (1 lb/mm) to about 88 N/mm (20 lbs/mm),from about 4.4 N/mm (1 lb/mm) to about 66 N/mm (15 lbs/mm), or fromabout 8.8 N/mm (2 lb/mm) to about 44 N/mm (10 lbs/mm).

Embodiment L44 is the method of any one of embodiments L1 to L43,wherein the shaped porous carbon product has a mechanical piece crushstrength greater than about 22 N (5 lbs), greater than about 36 N (8lbs), or greater than about 44 N (10 lbs).

Embodiment L45 is the method of any one of embodiments L1 to L43,wherein the shaped porous carbon product has a mechanical piece crushstrength from about 22 N (5 lbs) to about 88 N (20 lbs), from about 22 N(5 lbs) to about 66 N (15 lbs), or from about 33 N (7.5 lbs) to about 66N (15 lbs).

Embodiment L46 is the method of any one of embodiments L1 to L45,wherein the shaped porous carbon product has a mean diameter of at leastabout 50 μm, at least about 500 μm, at least about 1,000 μm, or at leastabout 10,000 μm.

Embodiment L47 is the method of any one of embodiments L1 to L46,wherein the shaped porous carbon product has the carbon black content ofat least about 35 wt. %, at least about 40 wt. %, at least about 45 wt.%, at least about 50 wt. %, at least about 55 wt. %, at least about 60wt. %, at least about 65 wt. %, or at least about 70 wt. %.

Embodiment L48 is the method of any one of embodiments L1 to L46,wherein the shaped porous carbon product has the carbon black contentfrom about 35 wt. % to about 80 wt. %, from about 35 wt. % to about 75wt. %, from about 40 wt. % to about 80 wt. %, or from about 40 wt. % toabout 75 wt. %.

Embodiment L49 is the method of any one of embodiments L1 to L48,wherein the carbon black comprises conductive carbon black.

Embodiment L50 is the method of any one of embodiments L1 to L49,wherein the carbon black comprises nonconductive carbon black.

Embodiment L51 is the method of embodiment L50, wherein the shapedporous carbon product does not exhibit a conductivity that is suitablefor a conductive electrode.

Embodiment L52 is the method of embodiment L50 or L51, wherein theshaped porous carbon product comprises nonconductive carbon black andless than about 50%, less than about 40%, less than about 30%, less thanabout 20%, less than about 10%, less than about 5%, or less than about1% conductive carbon black based on the total weight of the carbon blackin shaped porous carbon product.

Embodiment L53 is the method of any one of embodiments L1 to L48,wherein the shaped porous carbon product comprises carbon blackconsisting essentially of nonconductive carbon black.

Embodiment L54 is the method of any one of embodiments L1 to L48,wherein the shaped porous carbon product comprises carbon blackconsisting of nonconductive carbon black.

Embodiment L55 is the method of any one of embodiments L1 to L54,wherein the water soluble organic binder comprises a carbohydrate orderivative thereof.

Embodiment L56 is the method of embodiment L55, wherein derivatives ofcarbohydrates are selected from the group consisting of alginic acid,pectin, aldonic acids, aldaric acids, uronic acids, sugar alcohols, andsalts, oligomers, and polymers thereof.

Embodiment L57 is the method of any one of embodiments L1 to L56,wherein the water soluble organic binder comprises a monosaccharideselected from the group consisting of a glucose, a fructose, hydratethereof, syrup thereof, and combinations thereof.

Embodiment L58 is the method of any one of embodiments L1 to L57,wherein the water soluble organic binder comprises a saccharide selectedfrom the group consisting of maltose, sucrose, syrups thereof, solublestarches, soluble gums, and combinations thereof.

Embodiment L59 is the method of any one of embodiments L1 to L58,wherein the water soluble organic binder comprises a cellulosiccompound.

Embodiment L60 is the method of embodiment L59, wherein the cellulosiccompound comprises hydroxyethylcellulose, hydroxypropylcellulose,hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, orcarboxymethylcellulose.

Embodiment L61 is the method of any one of embodiments L59 or L60,wherein the cellulosic compound comprises alginic acid, pectin, or asalt thereof.

Embodiment L62 is the method of any one of embodiments L1 to L61,wherein the water soluble organic binder comprises a water solublepolymer or copolymer.

Embodiment L63 is the method of embodiment L62, wherein the watersoluble polymer or copolymer is selected from the group consisting ofpolyacrylic acid, polyvinyl alcohols, polyvinyl acetates, polyacrylatesand copolymers derived therefrom.

Embodiment L64 is the method of any one of embodiments L1 to L63,wherein the water soluble organic binder is selected from the groupconsisting of water soluble celluloses; water soluble alcohols; watersoluble acetals; water soluble acids; polyvinyl acrylic acids; andsalts, esters, oligomers, or polymers of any of these.

Embodiment L65 is the method of any one of embodiments L1 to L64,wherein the water soluble organic binder comprises a saccharide incombination with one or more water soluble celluloses; water solublealcohols; water soluble acetals; water soluble acids; polyvinyl acrylicacids; or salts, esters, oligomers, or polymers of any of these.

Embodiment L66

The method of embodiment L65, wherein the saccharide comprises amonosaccharide.

Embodiment L67 is the method of embodiment L66, wherein the watersoluble cellulose comprises hydroxyethylcellulose or methylcellulose andthe monosaccharide comprises a glucose, fructose or hydrate thereof.

Embodiment L68 is the method of embodiment L67, wherein the watersoluble cellulose comprises hydroxyethylcellulose and the monosaccharidecomprises a glucose or hydrate thereof.

Embodiment L69 is the method of any one of embodiments L64 to L68,wherein the water soluble alcohol is selected from the group consistingof sorbitol, mannitol, xylitol and a polyvinyl alcohol.

Embodiment L70

The method of any one of embodiments L64 to L69, wherein the watersoluble acid is selected from the group consisting of stearic acid,pectin, alginic acid, polyacrylic acid, and salts thereof.

Embodiment L71 is the method of any one of embodiments L1 to L70,wherein the shape of the shaped carbon black product is selected fromthe group consisting of spheres, beads, cylinders, pellets, multi-lobedshapes, rings, stars, ripped cylinders, triholes, alphas, and wheels.

Embodiment L72 is the method of any one of embodiments L1 to L71,wherein the sulfur content of the shaped porous carbon product is nogreater than about 1 wt. % or no greater than about 0.1 wt. %.

Embodiment L73 is the method of any one of embodiments L1 to L72,wherein the carbon black has a BET specific surface area from about 20m²/g to about 500 m²/g or from about 25 m²/g to about 250 m²/g, fromabout 25 m²/g to about 250 m²/g, from about 25 m²/g to about 225 m²/g,from about 25 m²/g to about 200 m²/g, from about 25 m²/g to about 175m²/g, from about 25 m²/g to about 150 m²/g, from about 25 m²/g to about125 m²/g, or from about 25 m²/g to about 100 m²/g.

Embodiment L74 is the method of any one of embodiments L1 to L72,wherein the carbon black has a BET specific surface area from about 30m²/g to about 250 m²/g, 30 m²/g to about 225 m²/g, from about 30 m²/g toabout 200 m²/g, from about 30 m²/g to about 175 m²/g, from about 30 m²/gto about 150 m²/g, from about 30 m²/g to about 125 m²/g, or from about30 m²/g to about 100 m²/g.

Embodiment L75 is the method of any one of embodiments L1 to L74,wherein the carbon black has a mean pore diameter greater than about 10nm, greater than about 12 nm, or greater than about 14 nm.

Embodiment L76 is the method of any one of embodiments L1 to L74,wherein the carbon black has a mean pore diameter from about 10 nm toabout 100 nm, from about 10 nm to about 70 nm, from 10 nm to about 50nm, or from about 10 nm to about 25 nm.

Embodiment L77 is the method of any one of embodiments L1 to L76,wherein the carbon black has a specific pore volume greater than about0.1 cm³/g, greater than about 0.2 cm³/g, or greater than about 0.3cm³/g.

Embodiment L78 is the method of any one of embodiments L1 to L76,wherein the carbon black has a specific pore volume of from about 0.1cm³/g to about 1.5 cm³/g, from about 0.1 cm³/g to about 0.9 cm³/g, fromabout 0.1 cm³/g to about 0.8 cm³/g, from about 0.1 cm³/g to about 0.7cm³/g, from about 0.1 cm³/g to about 0.6 cm³/g, from about 0.1 cm³/g toabout 0.5 cm³/g, from about 0.2 cm³/g to about 1 cm³/g, from about 0.2cm³/g to about 0.9 cm³/g, from about 0.2 cm³/g to about 0.8 cm³/g, fromabout 0.2 cm³/g to about 0.7 cm³/g, from about 0.2 cm³/g to about 0.6cm³/g, from about 0.2 cm³/g to about 0.5 cm³/g, from about 0.3 cm³/g toabout 1 cm³/g, from about 0.3 cm³/g to about 0.9 cm³/g, from about 0.3cm³/g to about 0.8 cm³/g, from about 0.3 cm³/g to about 0.7 cm³/g, fromabout 0.3 cm³/g to about 0.6 cm³/g, or from about 0.3 cm³/g to about 0.5cm³/g.

Embodiment M1 is a catalyst composition comprising a shaped porouscarbon support and a catalytically active component comprising platinumand at least one metal (M2) selected from the group consisting ofmolybdenum, lanthanum, samarium, yttrium, tungsten, and rhenium at asurface of the support.

Embodiment M2 is the catalyst composition of embodiment M1, wherein theshaped porous carbon support comprises the shaped porous carbon productof any one of embodiments A1 to A49 or B1 to B33.

Embodiment M3 is the catalyst composition of embodiment M1 or M2,wherein the catalytically active component of the catalyst compositioncomprises platinum and tungsten.

Embodiment M4 is the catalyst composition of any one of embodiments M1to M3, wherein the total metal loading of the catalyst composition isfrom about 0.1% to about 10%, or from 0.2% to 10%, or from about 0.2% toabout 8%, or from about 0.2% to about 5%, of the total weight of thecatalyst.

Embodiment M5 is the catalyst composition of any one of embodiments M1to M4, wherein the molar ratio of platinum to M2 metal is from about20:1 to about 1:10, from about 10:1 to about 1:5, or from about 8:1 toabout 1:2.

Embodiment N1 is a process for the selective hydrodeoxygenation of1,2,6-hexanetriol to 1,6-hexanediol comprising:

reacting the 1,2,6-hexanetriol with hydrogen in the presence of acatalyst composition of any one of embodiments M1 to M5 to form1,6-hexanediol.

Embodiment N2 is the process of embodiment N1, wherein the reaction of1,2,6-hexanetriol to 1,6-hexanediol is conducted at a temperature in therange of about 60° C. to about 200° C. or about 120° C. to about 180° C.and a partial pressure of hydrogen in the range of about 200 psig toabout 2000 psig or about 500 psig to about 2000 psig.

Embodiment P1 is a catalyst composition comprising a shaped porouscarbon support and a catalytically active component comprisingruthenium.

Embodiment P2 is the catalyst composition of embodiment P1, wherein theshaped porous carbon support comprises the shaped porous carbon productof any one of embodiments A1 to A49 or B1 to B33.

Embodiment P3 is the catalyst composition of embodiment P1 or P2,wherein the catalytically active component of the catalyst compositionfurther comprises rhenium.

Embodiment P4 is the catalyst composition of any one of embodiments P1to P3, wherein the total metal loading of the catalyst composition isfrom about 0.1% to about 10%, from about 1% to about 6%, or from about1% to about 5% of the total weight of the catalyst.

Embodiment P5 is the catalyst composition of any one of embodiments P1to P4, wherein the catalytically active component of the catalystcomposition further comprises rhenium and the molar ratio ofruthenium:rhenium is from about 20:1 to about 4:1, from about 10:1 toabout 4:1, or from about 8:1 to about 4:1.

Embodiment P6 is the catalyst composition of any one of embodiments P1to P5, wherein the catalytically active component of the catalystcomposition further comprises nickel.

Embodiment Q1 is a process for the selective amination of 1,6-hexanediolto 1,6-hexamethylenediamine comprising reacting the 1,6-hexanediol withan amine in the presence of a catalyst composition of any one ofembodiments P1 to P6 to form 1,6-hexamethylenediamine.

Embodiment Q2 is the process of embodiment Q1, wherein the aminecomprises ammonia.

Embodiment Q3 is the process of embodiment Q2, wherein the molar ratioof ammonia to 1,6-hexanediol is at least about 40:1, at least about30:1, at least about 20:1, or in the range of from about 40:1 to about5:1, or from about 30:1 to about 10:1.

Embodiment Q4 is the process of any one of embodiments Q1 to Q3, whereinthe reaction of 1,6-hexanediol with amine in the presence of thecatalyst composition is carried out at a temperature less than or equalto about 200° C., less than or equal to about 100° C., or in the rangeof about 100° C. to about 180° C., or about 140° C. to about 180° C.

Embodiment Q5 is the process of any one of embodiments Q1 to Q4, whereinthe reaction of 1,6-hexanediol with amine in the presence of thecatalyst composition is conducted at a pressure not exceeding about 1500psig, in the range of about 200 psig to about 1500 psig, of about 400psig to about 1200 psig, of about 400 psig to about 1000 psig.

Embodiment Q6 is the process of any one of embodiments Q1 to Q5, whereinthe reaction of 1,6-hexanediol with amine in the presence of thecatalyst composition is conducted with 1,6-hexanediol and ammonia at atemperature in the range of about 100° C. to about 180° C. and apressure in the range of about 200 psig to about 1500 psig.

Embodiment Q7 is the process of any one of embodiments Q1 to Q6, whereinthe 1,6-hexanediol and amine are reacted in the presence of hydrogen andthe catalyst composition, and the hydrogen partial pressure is equal toor less than about 100 psig.

Embodiment Q8 is the process of any one of embodiments Q1 to Q7, whereinat least 20%, at least 30%, at least 40%, at least 50%, at least 60%, orat least 70% of the product mixture resulting from a single passreaction of 1,6-hexanediol with amine (e.g., ammonia) in the presence ofthe catalyst composition is 1,6-hexamethylenediamine.

Embodiment AA1 is a shaped porous carbon product:

(a) carbon black and

(b) a carbonized binder comprising a carbonization product of a watersoluble organic binder and wherein the shaped porous carbon product hasa BET specific surface area from about 20 m²/g to about 500 m²/g, a meanpore diameter greater than about 5 nm, a specific pore volume greaterthan about 0.1 cm³/g, a carbon black content of at least about 35 wt. %,and a carbonized binder content from about 20 wt. % to about 50 wt. %,and wherein the shaped porous carbon product has a radial piece crushstrength greater than about 4.4 N/mm (1 lb/mm) and/or a mechanical piececrush strength greater than about 22 N (5 lbs).

Embodiment AA2 is the shaped porous carbon product of embodiment AA1,wherein the shaped porous carbon product has a BET specific surface areafrom about 20 m²/g to about 350 m²/g, from about 20 m²/g to about 250m²/g, from about 20 m²/g to about 225 m²/g, from about 20 m²/g to about200 m²/g, from about 20 m²/g to about 175 m²/g, from about 20 m²/g toabout 150 m²/g, from about 20 m²/g to about 125 m²/g, or from about 20m²/g to about 100 m²/g, from about 25 m²/g to about 500 m²/g, from about25 m²/g to about 350 m²/g, from about 25 m²/g to about 250 m²/g, fromabout 25 m²/g to about 225 m²/g, from about 25 m²/g to about 200 m²/g,from about 25 m²/g to about 175 m²/g, from about 25 m²/g to about 150m²/g, from about 25 m²/g to about 125 m²/g, or from about 25 m²/g toabout 100 m²/g.

Embodiment AA3 is the shaped porous carbon product of embodiment AA1,wherein the shaped porous carbon product has a BET specific surface areafrom about 30 m²/g to about 500 m²/g, from about 30 m²/g to about 350m²/g, from about 30 m²/g to about 250 m²/g, from about 30 m²/g to about225 m²/g, from about 30 m²/g to about 200 m²/g, from about 30 m²/g toabout 175 m²/g, from about 30 m²/g to about 150 m²/g, from about 30 m²/gto about 125 m²/g, or from about 30 m²/g to about 100 m²/g.

Embodiment AA3 is the shaped porous carbon product of any one ofembodiments 90 to 92, wherein the shaped porous carbon product has amean pore diameter greater than about 10 nm, greater than about 12 nm,or greater than about 14 nm.

Embodiment AA4 is the shaped porous carbon product of any one ofembodiments AA1 to 92, wherein the shaped porous carbon product has amean pore diameter from about 5 nm to about 100 nm, from about 5 nm toabout 70 nm, from 5 nm to about 50 nm, from about 5 nm to about 25 nm,from about 10 nm to about 100 nm, from about 10 nm to about 70 nm, from10 nm to about 50 nm, or from about 10 nm to about 25 nm.

Embodiment AA5 is the shaped porous carbon product of any one ofembodiments AA1 to AA4, wherein the shaped porous carbon product has aspecific pore volume of the pores having a diameter of 1.7 nm to 100 nmas measured by the BJH method that is greater than about 0.2 cm³/g orgreater than about 0.3 cm³/g.

Embodiment AA6 is the shaped porous carbon product of any one ofembodiments AA1 to AA4, wherein the shaped porous carbon product has aspecific pore volume of the pores having a diameter of 1.7 nm to 100 nmas measured by the BJH method that is from about 0.1 cm³/g to about 1.5cm³/g, from about 0.1 cm³/g to about 0.9 cm³/g, from about 0.1 cm³/g toabout 0.8 cm³/g, from about 0.1 cm³/g to about 0.7 cm³/g, from about 0.1cm³/g to about 0.6 cm³/g, from about 0.1 cm³/g to about 0.5 cm³/g, fromabout 0.2 cm³/g to about 1 cm³/g, from about 0.2 cm³/g to about 0.9cm³/g, from about 0.2 cm³/g to about 0.8 cm³/g, from about 0.2 cm³/g toabout 0.7 cm³/g, from about 0.2 cm³/g to about 0.6 cm³/g, from about 0.2cm³/g to about 0.5 cm³/g, from about 0.3 cm³/g to about 1 cm³/g, fromabout 0.3 cm³/g to about 0.9 cm³/g, from about 0.3 cm³/g to about 0.8cm³/g, from about 0.3 cm³/g to about 0.7 cm³/g, from about 0.3 cm³/g toabout 0.6 cm³/g, or from about 0.3 cm³/g to about 0.5 cm³/g.

Embodiment AA7 is the shaped porous carbon product of any one ofembodiments AA1 to AA6, wherein at least about 35%, at least about 40%,at least about 45%, or at least about 50% of the pore volume of theshaped porous carbon product, as measured by the BJH method on the basisof pores having a diameter from 1.7 nm to 100 nm, is attributable topores having a mean pore diameter of from about 10 nm to about 50 nm.

Embodiment AA8 is the shaped porous carbon product of any one ofembodiments AA1 to AA6, wherein from about 35% to about 80%, from about35% to about 75%, from about 35% to about 65%, from about 40% to about80%, from about 40% to about 75%, or from about 40% to about 70% of thepore volume of the shaped porous carbon product, as measured by the BJHmethod on the basis of pores having a diameter from 1.7 nm to 100 nm, isattributable to pores having a mean pore diameter of from about 10 nm toabout 50 nm.

Embodiment AA9 is the shaped porous carbon product of any one ofembodiments AA1 to AA8, wherein at least about 50%, at least about 60%,at least about 70%, at least about 80%, or at least about 90% of thepore volume of the shaped porous carbon product, as measured by the BJHmethod on the basis of pores having a diameter from 1.7 nm to 100 nm, isattributable to pores having a mean pore diameter of from about 10 nm toabout 100 nm.

Embodiment AA10 is the shaped porous carbon product of any one ofembodiments AA1 to AA8, wherein from about 50% to about 95%, from about50% to about 90%, from about 50% to about 80%, from about 60% to about95%, from about 60% to about 90%, from about 60% to about 80%, fromabout 70% to about 95%, from about 70% to about 90%, from about 70% toabout 80%, from about 80% to about 95%, or from about 80% to about 90%of the pore volume of the shaped porous carbon product, as measured bythe BJH method on the basis of pores having a diameter from 1.7 nm to100 nm, is attributable to pores having a mean pore diameter of fromabout 10 nm to about 100 nm.

Embodiment AA11 is the shaped porous carbon product of any one ofembodiments AA1 to AA10, wherein no more than about 10%, no more thanabout 5%, or no more than about 1% of the pore volume of the shapedporous carbon product, as measured by the BJH method on the basis ofpores having a diameter from 1.7 nm to 100 nm, is attributable to poreshaving a mean pore diameter less than 10 nm, less than 5 nm, or lessthan 3 nm.

Embodiment AA12 is the shaped porous carbon product of any one ofembodiments AA1 to AA10, wherein from about 0.1% to about 10%, fromabout 0.1% to about 5%, from about 0.1% to about 1%, from about 1% toabout 10%, or from about 1% to about 5% of the pore volume of the shapedporous carbon product, as measured by the BJH method on the basis ofpores having a diameter from 1.7 nm to 100 nm, is attributable to poreshaving a mean pore diameter less than 10 nm, less than 5 nm, or lessthan 3 nm.

Embodiment AA13 is the shaped porous carbon product of any one ofembodiments AA1 to AA12, wherein the shaped porous carbon product has apore size distribution such that the peak of the distribution is at adiameter greater than about 5 nm, greater than about 7.5 nm, greaterthan about 10 nm, greater than about 12.5 nm, greater than about 15 nm,or greater than about 20 nm.

Embodiment AA14 is the shaped porous carbon product of any one ofembodiments AA1 to AA13, wherein the shaped porous carbon product has apore size distribution such that the peak of the distribution is at adiameter less than about 100 nm, less than about 90 nm, less than about80 nm, or less than about 70 nm.

Embodiment AA15 is the shaped porous carbon product of any one ofembodiments AA1 to AA14, wherein the shaped porous carbon product has aradial piece crush strength greater than about 8.8 N/mm (2 lbs/mm) orgreater than about 13.3 N/mm (3 lbs/mm).

Embodiment AA16 is the shaped porous carbon product of any one ofembodiments AA1 to AA14, wherein the shaped porous carbon product has aradial piece crush strength from about 4.4 N/mm (1 lb/mm) to about 88N/mm (20 lbs/mm), from about 4.4 N/mm (1 lb/mm) to about 66 N/mm (15lbs/mm), or from about 8.8 N/mm (2 lbs/mm) to about 44 N/mm (10 lbs/mm).

Embodiment AA17 is the shaped porous carbon product of any one ofembodiments AA1 to AA16, wherein the shaped porous carbon product has amechanical piece crush strength greater than about 22 N (5 lbs), greaterthan about 36 N (8 lbs), or greater than about 44 N (10 lbs).

Embodiment AA18 is the shaped porous carbon product of any one ofembodiments AA1 to AA16, wherein the shaped porous carbon product has amechanical piece crush strength from about 22 N (5 lbs) to about 88 N(20 lbs), from about 22 N (5 lbs) to about 66 N (15 lbs), or from about33 N (7.5 lbs) to about 66 N (15 lbs).

Embodiment AA19 is the shaped porous carbon product of any one ofembodiments AA1 to AA18, wherein the shaped porous carbon product has amean diameter of at least about 50 μm, at least about 500 μm, at leastabout 1,000 μm, or at least about 10,000 μm.

Embodiment AA20 is the shaped porous carbon product of any one ofembodiments AA1 to AA19, wherein the carbon black content of the shapedporous carbon product is at least about 40 wt. %, at least about 45 wt.%, at least about 50 wt. %, at least about 55 wt. %, at least about 60wt. %, at least about 65 wt. %, or at least about 70 wt. %.

Embodiment AA21 is the shaped porous carbon product of any one ofembodiments AA1 to AA19, wherein the carbon black content of the shapedporous carbon product is from about 35 wt. % to about 80 wt. %, fromabout 35 wt. % to about 75 wt. %, from about 40 wt. % to about 80 wt. %,or from about 40 wt. % to about 75 wt. %.

Embodiment AA22 is the shaped porous carbon product of any one ofembodiments AA1 to AA20, wherein the shaped porous carbon product has acarbonized binder content from about 10 wt. % to about 50 wt. %, fromabout 20 wt. % to about 50 wt. %, from about 25 wt. % to about 40 wt. %,or from about 25 wt. % to about 35 wt. %.

Embodiment AA23 is the shaped porous carbon product of any one ofembodiments AA1 to AA22, wherein the composition exhibits a rotatingdrum attrition index as measured in accordance with ASTM D4058-96 suchthat the percent retained is greater than about 85%, greater than about90%, greater than about 92%, or greater than about 95%.

Embodiment AA24 is the shaped porous carbon product of embodiment AA23,wherein the composition exhibits a rotating drum attrition index asmeasured in accordance with ASTM D4058-96 such that the percent retainedis greater than about 97%, or greater than about 99% by weight.

Embodiment AA25 is the shaped porous carbon product of any one ofembodiments AA1 to AA24, wherein the composition exhibits a horizontalagitation sieve abrasion loss of less than about 5%, or less than about3%.

Embodiment AA26 is the shaped porous carbon product of embodiment AA25,wherein the composition exhibits a horizontal agitation sieve abrasionloss of less than about 2%, less than about 1%, less than about 0.5%,less than about 0.2%, less than about 0.1%, less than about 0.05%, orless than about 0.03% by weight.

Embodiment AA27 is the shaped porous carbon product of any one ofembodiments AA1 to AA26, wherein the binder comprises a saccharideselected from the group consisting of a monosaccharide, a disaccharide,an oligosaccharide, or any combination thereof.

Embodiment AA28 is the shaped porous carbon product of any one ofembodiments AA1 to AA27, wherein the binder comprises a monosaccharide.

Embodiment AA29 is the shaped porous carbon product of embodiment AA35or AA28, wherein the monosaccharide is selected from the groupconsisting of glucose, fructose, hydrate thereof, syrup thereof, andcombinations thereof.

Embodiment AA30 is the shaped porous carbon product of any one ofembodiments AA1 to AA29, wherein the binder comprises a disaccharide.

Embodiment AA31 is the shaped porous carbon product of any one ofembodiments AA35 to AA30, wherein the disaccharide is selected from thegroup consisting of maltose, sucrose, syrup thereof, and combinationsthereof.

Embodiment AA32 is the shaped porous carbon product of embodiment AA1 toAA31, wherein the binder comprises a polymeric carbohydrate, derivativeof a polymeric carbohydrate, or a non-carbohydrate synthetic polymer, orany combination thereof.

Embodiment AA33 is the shaped porous carbon product of any one ofembodiments AA1 to AA32, wherein the binder comprises a polymericcarbohydrate, derivative of a polymeric carbohydrate, or any combinationthereof.

Embodiment AA34 is the shaped porous carbon product of any one ofembodiments AA40 or AA33, wherein the polymeric carbohydrate orderivative of the polymeric carbohydrate comprises a cellulosiccompound.

Embodiment AA35 is the shaped porous carbon product of embodiment AA34,wherein the cellulosic compound is selected from the group consisting ofmethylcellulose, ethylcellulose, ethylmethylcellulose,hydroxyethylcellulose, hydroxypropylcellulose,methylhydroxyethylcellulose, ethylhydroxyethylcellulose,hydroxypropylmethylcellulose, carboxymethylcellulose, and mixturesthereof.

Embodiment AA36 is the shaped porous carbon product of any one ofembodiments AA40 to AA35, wherein the polymeric carbohydrate orderivative of the polymeric carbohydrate derivative is selected from thegroup consisting of alginic acid, pectin, aldonic acids, aldaric acids,uronic acids, sugar alcohols, and salts, oligomers, and polymersthereof.

Embodiment AA37 is the shaped porous carbon product of any one ofembodiments AA40 to AA36, wherein the polymeric carbohydrate orderivative of the polymeric carbohydrate comprises a starch.

Embodiment AA38 is the shaped porous carbon product of any one ofembodiments AA40 to AA37, wherein the polymeric carbohydrate orderivative of the polymeric carbohydrate comprises a soluble gum.

Embodiment AA39 is the shaped porous carbon product of any one ofembodiments AA1 to AA38, wherein the binder comprises a non-carbohydratesynthetic polymer.

Embodiment AA40 is the shaped porous carbon product of any one ofembodiments AA39, wherein the non-carbohydrate synthetic polymer isselected from the group consisting of polyacrylic acid, polyvinylalcohols, polyvinylpyrrolidones, polyvinyl acetates, polyacrylates,polyethers, and copolymers derived therefrom.

Embodiment AA41 is the shaped porous carbon product of any one ofembodiments AA1 to AA40, wherein the binder comprises one or morecomponents selected from the group consisting of water solublecelluloses; water soluble alcohols; water soluble acetals; water solubleacids; polyvinyl acrylic acids; polyethers; and salts, esters,oligomers, or polymers of any of these.

Embodiment AA42 is the shaped porous carbon product of any one ofembodiments AA1 to AA41, wherein the binder comprises a saccharideselected from the group consisting of glucose, fructose or hydratethereof and a polymeric carbohydrate or derivative of the polymericcarbohydrate selected from the group consisting ofhydroxyethylcellulose, methylcellulose, and starch.

Embodiment AA43 is the shaped porous carbon product of any one ofembodiments AA1 to AA42, wherein the weight ratio of (i) the saccharideto (ii) the polymeric carbohydrate, derivative of the polymericcarbohydrate, or the non-carbohydrate synthetic polymer, or combinationthereof is from about 5:1 to about 50:1, from about 10:1 to about 25:1,or from about 10:1 to about 20:1.

Embodiment BB1 is a catalyst composition comprising the shaped porouscarbon product of any one of embodiments AA1 to AA51 as a catalystsupport and a catalytically active component or precursor thereof at asurface of the support.

Embodiment BB2 is the catalyst composition of embodiment BB1, whereinthe catalytically active component or precursor thereof comprises ametal.

Embodiment BB3 is the catalyst composition of embodiment BB2, whereinthe metal comprises at least one d-block metal.

Embodiment BB4 is the catalyst composition of embodiment BB2, whereinthe metal comprises at least one metal selected from groups VI, V, VI,VII, VIII, IX, X, XI, XII, and XIII.

Embodiment BB5 is the catalyst composition of embodiment BB2, whereinthe metal is selected from the group consisting of cobalt, nickel,copper, zinc, iron, vanadium, molybdenum, manganese, barium, ruthenium,rhodium, rhenium, palladium, silver, osmium, iridium, platinum, gold,and combinations thereof.

Embodiment BB6 is the catalyst composition of embodiment BB2, whereinthe metal comprises nickel.

Embodiment CC1 is a method of preparing a catalyst composition, themethod comprising depositing a catalytically active component orprecursor thereof at a surface of the shaped porous carbon product ofany one of embodiments AA1 to AA51.

Embodiment CC2 is the catalyst composition of embodiment CC1, whereinthe catalytically active component or precursor thereof comprises ametal.

Embodiment CC3 is the catalyst composition of embodiment CC2, whereinthe metal comprises at least one d-block metal.

Embodiment CC4 is the catalyst composition of embodiment CC2, whereinthe metal comprises at least one metal selected from groups VI, V, VI,VII, VIII, IX, X, XI, XII, and XIII.

Embodiment CC5 is the catalyst composition of embodiment CC2, whereinthe metal is selected from the group consisting of cobalt, nickel,copper, zinc, iron, vanadium, molybdenum, manganese, barium, ruthenium,rhodium, rhenium, palladium, silver, osmium, iridium, platinum, gold,and combinations thereof.

Embodiment DD1 is a method of preparing a shaped porous carbon product,the method comprising:

mixing and heating water and a water soluble organic binder to form abinder solution, wherein the water and binder are heated to atemperature of at least about 50° C., and wherein the binder comprises:(i) a saccharide selected from the group consisting of a monosaccharide,a disaccharide, an oligosaccharide, a derivative thereof, and anycombination thereof and (ii) a polymeric carbohydrate, a derivative of apolymeric carbohydrate, or a non-carbohydrate synthetic polymer, or anycombination thereof;

mixing carbon black with the binder solution to produce a carbon blackmixture;

forming the carbon black mixture to produce a shaped carbon blackcomposite; and

heating the shaped carbon black composite to carbonize the binder to awater insoluble state and to produce the shaped porous carbon product.

Embodiment DD2 is a method of preparing a shaped porous carbon product,the method comprising:

mixing water, carbon black, and a water soluble organic binder to form acarbon black mixture, wherein the binder comprises: (i) a saccharideselected from the group consisting of a monosaccharide, a disaccharide,an oligosaccharide, a derivative thereof, and any combination thereofand (ii) a polymeric carbohydrate, a derivative of a polymericcarbohydrate, or a non-carbohydrate synthetic polymer, or anycombination thereof;

forming the carbon black mixture to produce a shaped carbon blackcomposite; and

heating the shaped carbon black composite to carbonize the binder to awater insoluble state and to produce the shaped porous carbon product.

Embodiment DD3 is a method of preparing a shaped porous carbon product,the method comprising:

mixing water, carbon black, and a binder to form a carbon black mixture,wherein the binder comprises a saccharide selected from the groupconsisting of a monosaccharide, a disaccharide, an oligosaccharide, aderivative thereof, or any combination thereof and wherein the weightratio of the binder to carbon black in the carbon black mixture is atleast about 1:4, at least about 1:3, at least about 1:2, at least about1:1, or at least 1.5:1;

forming the carbon black mixture to produce a shaped carbon blackcomposite; and

heating the shaped carbon black composite to carbonize the binder to awater insoluble state and to produce the shaped porous carbon product.

Embodiment DD4 is a method of preparing a shaped porous carbon product,the method comprising:

mixing water, carbon black, and a binder to form a carbon black mixture,wherein the binder comprises a saccharide selected from the groupconsisting of a monosaccharide, a disaccharide, an oligosaccharide, aderivative thereof, or any combination thereof and wherein the watercontent of the carbon black mixture is no more than about 80% by weight,no more than about 55% by weight, no more than about 40% by weight, orno more than about 25% by weight;

forming the carbon black mixture to produce the shaped carbon blackcomposite; and

heating the shaped carbon black composite to carbonize the binder to awater insoluble state and to produce a shaped porous carbon product.

Embodiment DD5 is the method of any one of embodiments DD1 to DD4,wherein the water and water soluble organic binder are mixed and heatedto form a binder solution prior to mixing with carbon black.

Embodiment DD6 is the method of embodiment DD9, wherein the water andbinder are heated to a temperature of at least about 50° C., at leastabout 60° C., or at least about 70° C.

Embodiment DD7 is the method of embodiment DD1 or DD6, wherein the waterand binder are heated to a temperature of from about 50° C. to about 95°C., from about 50° C. to about 90° C., or from about 60° C. to about 85°C.

Embodiment DD8 is the method of any one of embodiments DD1 or DD5 toDD7, further comprising cooling the binder solution prior to mixing withcarbon black or prior to forming the shaped carbon black composite.

Embodiment DD9 is the method of any of embodiments DD1 or DD5 to DD8,wherein the water content of the carbon black mixture is no more thanabout 80% by weight, no more than about 55% by weight, no more thanabout 40% by weight, or no more than about 25% by weight.

Embodiment DD10 is the method of any of embodiments DD1 or DD5 to DD8,wherein the water content of the carbon black mixture is from about 5wt. % to about 70 wt. % or from about 5 wt. % to about 55 wt. %.

Embodiment DD11 is the method of any of embodiments DD1 or DD5 to DD10,wherein the water content of the carbon black mixture is from about 5wt. % to about 40 wt. % or from about 5 wt. % to about 25 wt. %.

Embodiment DD12 is the method of any one of embodiments DD1 to DD11further comprising pressing or kneading the carbon black mixture.

Embodiment DD13 is the method of embodiment DD12, wherein mixing of thewater, carbon black, and binder and pressing of the resulting carbonblack mixture is conducted simultaneously.

Embodiment DD14 is the method of embodiment DD13, wherein mixing of thewater, carbon black, and binder and pressing of the resulting carbonblack mixture is conducted using a mixer muller.

Embodiment DD15 is the method of any one of embodiments DD1 to DD14,wherein the carbon black mixture further comprises a forming adjuvant.

Embodiment DD16 is the method of embodiment DD15, wherein the formingadjuvant comprises a lubricant.

Embodiment DD17 is the method of embodiment DD15, wherein the formingadjuvant comprises lignin or derivative thereof.

Embodiment DD18 is the method of any one of embodiments DD1 to DD17,wherein the shaped carbon black composite is heated in an inert oroxidative atmosphere.

Embodiment DD19 is the method of embodiment DD18, wherein the atmosphereis an inert atmosphere.

Embodiment DD20 is the method of any one of embodiments DD1 to DD19,wherein the shaped carbon black composite is heated at a temperature offrom about 250° C. to about 1,000° C., from about 300° C. to about 900°C., from about 300° C. to about 850° C., from about 300° C. to about800° C., from about 350° C. to about 850° C., from about 350° C. toabout 800° C., from about 350° C. to about 700° C., from about 400° C.to about 850° C. or from about 400° C. to about 800° C.

Embodiment DD21 is the method of any one of embodiments DD1 to DD20,wherein the shaped carbon black composite is formed by extruding thecarbon black mixture.

Embodiment DD22 is the method of any one of embodiments DD1 to DD21,wherein the carbon black mixture is formed under a pressure of at leastabout 100 kPa (1 bar), or from about 100 kPa (1 bar) to about 10,000 kPa(100 bar), from about 500 kPa (5 bar) to 5,000 kPa (50 bar), or fromabout 1,000 kPa (10 bar) to about 3,000 kPa (30 bar).

Embodiment DD23 is the method of any one of embodiments DD1 to DD22,further comprising drying the shaped carbon black composite afterforming.

Embodiment DD24 is the method of embodiment DD23, wherein drying theshaped carbon black composite comprises heating at a temperature of fromabout 20° C. to about 150° C., from about 40° C. to about 120° C., orfrom about 60° C. to about 120° C.

Embodiment DD25 is the method of any one of embodiments DD1 to DD24,wherein the weight ratio of the binder to carbon black in the carbonblack mixture is at least about 1:4, at least about 1:3, at least about1:2, at least about 1:1, or at least 1.5:1.

Embodiment DD26 is the method of any one of embodiments DD1 to DD24,wherein the weight ratio of binder to carbon black in the carbon blackmixture is from about 1:4 to about 3:1, from about 1:4 to about 1:1,from about 1:3 to about 2:1, from about 1:3 to about 1:1, or about 1:1.

Embodiment DD27 is the method of any one of embodiments DD1 to DD26,wherein the carbon black content of the carbon black mixture is at leastabout 35 wt. %, at least about 40 wt. %, at least about 45 wt. %, atleast about 50 wt. %, at least about 55 wt. %, at least about 60 wt. %,at least about 65 wt. %, or at least about 70 wt. % on a dry weightbasis.

Embodiment DD28 is the method of any one of embodiments DD1 to DD26,wherein the carbon black content of the carbon black mixture is fromabout 35 wt. % to about 80 wt. %, from about 35 wt. % to about 75 wt. %,from about 40 wt. % to about 80 wt. %, or from about 40 wt. % to about75 wt. % on a dry weight basis.

Embodiment DD29 is the method of any one of embodiments DD1 to DD28,wherein the concentration of the binder in the carbon black mixture isat least about 10 wt. %, at least about 20 wt. %, at least about 25 wt.%, at least about 30 wt. %, at least about 35 wt. %, at least about 40wt. %, or at least 45 wt. % binder on a dry weight basis.

Embodiment DD30 is the method of any one of embodiments DD1 to DD28,wherein the concentration of the binder in the carbon black mixture isfrom about 10 wt. % to about 50 wt. %, from about 10 wt. % to about 45wt. %, from about 15 wt. % to about 50 wt. %, from about 20 wt. % toabout 50 wt. %, or from about 20 wt. % to about 45 wt. % on a dry weightbasis.

Embodiment DD31 is the method of any one of embodiments DD1 to DD30,wherein the binder comprises a saccharide selected from the groupconsisting of a monosaccharide, an oligosaccharide, or any combinationthereof.

Embodiment DD32 is the method of any one of embodiments DD1 to DD31,wherein the binder comprises a monosaccharide.

Embodiment DD33 is the method of any one of embodiments DD1 to DD32,wherein the monosaccharide is selected from the group consisting ofglucose, fructose, hydrate thereof, syrup thereof, and combinationsthereof.

Embodiment DD34 is the method of any one of embodiments DD1 to DD33,wherein the binder comprises a disaccharide.

Embodiment DD35 is the method of any one of embodiments DD1 to DD34,wherein the disaccharide is selected from the group consisting ofmaltose, sucrose, syrup thereof, and combinations thereof.

Embodiment DD36 is the method of any one of embodiments DD1 to DD35,wherein the binder comprises a polymeric carbohydrate.

Embodiment DD37 is the method of any one of embodiments DD1 to DD36,wherein the binder comprises a polymeric carbohydrate, derivative of apolymeric carbohydrate, or any combination thereof.

Embodiment DD38 is the method of any one of embodiments DD1 to DD37,wherein the polymeric carbohydrate or derivative of the polymericcarbohydrate comprises a cellulosic compound.

Embodiment DD39 is the method of embodiment DD38, wherein the cellulosiccompound is selected from the group consisting of methylcellulose,ethylcellulose, ethylmethylcellulose, hydroxyethylcellulose,hydroxypropylcellulose, methylhydroxyethylcellulose,ethylhydroxyethylcellulose, hydroxypropylmethylcellulose,carboxymethylcellulose, and mixtures thereof.

Embodiment DD40 is the method of any one of embodiments DD1 to DD39,wherein the polymeric carbohydrate or derivative of the polymericcarbohydrate derivative is selected from the group consisting of alginicacid, pectin, aldonic acids, aldaric acids, uronic acids, sugaralcohols, and salts, oligomers, and polymers thereof.

Embodiment DD41 is the method of any one of embodiments DD1 to DD40,wherein the polymeric carbohydrate or derivative of the polymericcarbohydrate comprises a starch.

Embodiment DD42 is the method of any one of embodiments DD1 to DD41,wherein the polymeric carbohydrate or derivative of the polymericcarbohydrate comprises a soluble gum.

Embodiment DD43 is the method of any one of embodiments DD1 to DD42,wherein the binder comprises a non-carbohydrate synthetic polymer.

Embodiment DD44 is the method of any one of embodiments DD1 to DD43,wherein the non-carbohydrate synthetic polymer is selected from thegroup consisting of polyacrylic acid, polyvinyl alcohols,polyvinylpyrrolidones, polyvinyl acetates, polyacrylates, polyethers,and copolymers derived therefrom.

Embodiment DD45 is the method of any one of embodiments DD1 to DD44,wherein the binder comprises one or more components selected from thegroup consisting of water soluble celluloses; water soluble alcohols;water soluble acetals; water soluble acids; polyvinyl acrylic acids;polyethers; and salts, esters, oligomers, or polymers of any of these.

Embodiment DD46 is the method of any one of embodiments DD1 to DD45,wherein the binder comprises a saccharide selected from the groupconsisting of glucose, fructose or hydrate thereof and a polymericcarbohydrate or derivative of the polymeric carbohydrate selected fromthe group consisting of hydroxyethylcellulose, methylcellulose, andstarch.

Embodiment DD47 is the method of any one of embodiments DD1 to DD46,wherein the weight ratio of (i) the saccharide to (ii) the polymericcarbohydrate, derivative of the polymeric carbohydrate, or thenon-carbohydrate synthetic polymer, or combination thereof is from about5:1 to about 50:1, from about 10:1 to about 25:1, or from about 10:1 toabout 20:1.

Embodiment DD48 is the method of any one of embodiments DD1 to DD47,wherein the carbon black mixture further comprises a porogen.

Embodiment DD49 is the method of embodiment DD48, wherein the porogencomprises a water soluble linear, branched, or cross-linked polymer.

Embodiment DD50 is the method any one of embodiments DD1 to DD49,wherein the water content of the carbon black mixture no more than about80% by weight, no more than about 55% by weight, no more than about 40%by weight, or no more than about 25% by weight.

Embodiment DD51 is the method any one of embodiments DD1 to DD49,wherein the water content of the carbon black mixture is from about 5wt. % to about 70 wt. %, from about 5 wt. % to about 55 wt. %, fromabout 5 wt. % to about 40 wt. %, or from about 5 wt. % to about 25 wt.%.

Embodiment DD52 is the method of any one of embodiments DD1 to DD51,wherein the shaped porous carbon product has a BET specific surface areafrom about 20 m²/g to about 500 m²/g, from about 20 m²/g to about 350m²/g, from about 20 m²/g to about 250 m²/g, from about 20 m²/g to about225 m²/g, from about 20 m²/g to about 200 m²/g, from about 20 m²/g toabout 175 m²/g, from about 20 m²/g to about 150 m²/g, from about 20 m²/gto about 125 m²/g, or from about 20 m²/g to about 100 m²/g, from about25 m²/g to about 500 m²/g, from about 25 m²/g to about 350 m²/g, fromabout 25 m²/g to about 250 m²/g, from about 25 m²/g to about 225 m²/g,from about 25 m²/g to about 200 m²/g, from about 25 m²/g to about 175m²/g, from about 25 m²/g to about 150 m²/g, from about 25 m²/g to about125 m²/g, or from about 25 m²/g to about 100 m²/g.

Embodiment DD53 is the method of any one of embodiments DD1 to DD52,wherein the shaped porous carbon product has a BET specific surface areafrom about 30 m²/g to about 500 m²/g, from about 30 m²/g to about 350m²/g, from about 30 m²/g to about 250 m²/g, from about 30 m²/g to about225 m²/g, from about 30 m²/g to about 200 m²/g, from about 30 m²/g toabout 175 m²/g, from about 30 m²/g to about 150 m²/g, from about 30 m²/gto about 125 m²/g, or from about 30 m²/g to about 100 m²/g.

Embodiment DD54 is the method of any one of embodiments DD1 to DD53,wherein the shaped porous carbon product has a mean pore diametergreater than about 5 nm, greater than about 10 nm, greater than about 12nm, or greater than about 14 nm.

Embodiment DD55 is the method of any one of embodiments DD1 to DD54,wherein the shaped porous carbon product has a mean pore diameter fromabout 5 nm to about 100 nm, from about 5 nm to about 70 nm, from 5 nm toabout 50 nm, from about 5 nm to about 25 nm, from about 10 nm to about100 nm, from about 10 nm to about 70 nm, from 10 nm to about 50 nm, orfrom about 10 nm to about 25 nm.

Embodiment DD56 is the method of any one of embodiments DD1 to DD55,wherein the shaped porous carbon product has a specific pore volume ofthe pores having a diameter of 1.7 nm to 100 nm as measured by the BJHmethod that is greater than about 0.1 cm³/g, greater than about 0.2cm³/g, or greater than about 0.3 cm³/g.

Embodiment DD57 is the method of any one of embodiments DD1 to DD55,wherein the shaped porous carbon product has a specific pore volume ofthe pores having a diameter of 1.7 nm to 100 nm as measured by the BJHmethod that is from about 0.1 cm³/g to about 1.5 cm³/g, from about 0.1cm³/g to about 0.9 cm³/g, from about 0.1 cm³/g to about 0.8 cm³/g, fromabout 0.1 cm³/g to about 0.7 cm³/g, from about 0.1 cm³/g to about 0.6cm³/g, from about 0.1 cm³/g to about 0.5 cm³/g, from about 0.2 cm³/g toabout 1 cm³/g, from about 0.2 cm³/g to about 0.9 cm³/g, from about 0.2cm³/g to about 0.8 cm³/g, from about 0.2 cm³/g to about 0.7 cm³/g, fromabout 0.2 cm³/g to about 0.6 cm³/g, from about 0.2 cm³/g to about 0.5cm³/g, from about 0.3 cm³/g to about 1 cm³/g, from about 0.3 cm³/g toabout 0.9 cm³/g, from about 0.3 cm³/g to about 0.8 cm³/g, from about 0.3cm³/g to about 0.7 cm³/g, from about 0.3 cm³/g to about 0.6 cm³/g, orfrom about 0.3 cm³/g to about 0.5 cm³/g.

Embodiment DD58 is the method of any one of embodiments DD1 to DD57,wherein at least about 35%, at least about 40%, at least about 45%, orat least about 50% of the pore volume of the shaped porous carbonproduct, as measured by the BJH method on the basis of pores having adiameter from 1.7 nm to 100 nm, is attributable to pores having a meanpore diameter of from about 10 nm to about 50 nm.

Embodiment DD59 is the method of any one of embodiments DD1 to DD57,wherein from about 35% to about 80%, from about 35% to about 75%, fromabout 35% to about 65%, from about 40% to about 80%, from about 40% toabout 75%, or from about 40% to about 70% of the pore volume of theshaped porous carbon product, as measured by the BJH method on the basisof pores having a diameter from 1.7 nm to 100 nm, is attributable topores having a mean pore diameter of from about 10 nm to about 50 nm.

Embodiment DD60 is the method of any one of embodiments DD1 to DD59,wherein at least about 50%, at least about 60%, at least about 70%, atleast about 80%, or at least about 90% of the pore volume of the shapedporous carbon product, as measured by the BJH method on the basis ofpores having a diameter from 1.7 nm to 100 nm, is attributable to poreshaving a mean pore diameter of from about 10 nm to about 100 nm.

Embodiment DD61 is the method of any one of embodiments DD1 to DD59,wherein from about 50% to about 95%, from about 50% to about 90%, fromabout 50% to about 80%, from about 60% to about 95%, from about 60% toabout 90%, from about 60% to about 80%, from about 70% to about 95%,from about 70% to about 90%, from about 70% to about 80%, from about 80%to about 95%, or from about 80% to about 90% of the pore volume of theshaped porous carbon product, as measured by the BJH method on the basisof pores having a diameter from 1.7 nm to 100 nm, is attributable topores having a mean pore diameter of from about 10 nm to about 100 nm.

Embodiment DD62 is the method of any one of embodiments DD1 to DD61,wherein no more than about 10%, no more than about 5%, or no more thanabout 1% of the pore volume of the shaped porous carbon product, asmeasured by the BJH method on the basis of pores having a diameter from1.7 nm to 100 nm, is attributable to pores having a mean pore diameterless than 10 nm, less than 5 nm, or less than 3 nm.

Embodiment DD63 is the method of any one of embodiments DD1 to DD61,wherein from about 0.1% to about 10%, from about 0.1% to about 5%, fromabout 0.1% to about 1%, from about 1% to about 10%, or from about 1% toabout 5% of the pore volume of the shaped porous carbon product, asmeasured by the BJH method on the basis of pores having a diameter from1.7 nm to 100 nm, is attributable to pores having a mean pore less than10 nm, less than 5 nm, or less than 3 nm.

Embodiment DD64 is the method of any one of embodiments DD1 to DD63,wherein the shaped porous carbon product has a pore size distributionsuch that the peak of the distribution is at a diameter greater thanabout 5 nm, greater than about 7.5 nm, greater than about 10 nm, greaterthan about 12.5 nm, greater than about 15 nm, or greater than about 20nm.

Embodiment DD65 is the method of any one of embodiments DD1 to DD64,wherein the shaped porous carbon product has a pore size distributionsuch that the peak of the distribution is at a diameter less than about100 nm, less than about 90 nm, less than about 80 nm, or less than about70 nm.

Embodiment DD66 is the method of any one of embodiments DD1 to DD65,wherein the shaped porous carbon product has a radial piece crushstrength greater than about 4.4 N/mm (1 lb/mm), greater than about 8.8N/mm (2 lbs/mm), or greater than about 13.3 N/mm (3 lbs/mm).

Embodiment DD67 is the method of any one of embodiments DD1 to DD65,wherein the shaped porous carbon product has a radial piece crushstrength from about 4.4 N/mm (1 lb/mm) to about 88 N/mm (20 lbs/mm),from about 4.4 N/mm (1 lb/mm) to about 66 N/mm (15 lbs/mm), or fromabout 8.8 N/mm (2 lb/mm) to about 44 N/mm (10 lbs/mm).

Embodiment DD68 is the method of any one of embodiments DD1 to DD67,wherein the shaped porous carbon product has a mechanical piece crushstrength greater than about 22 N (5 lbs), greater than about 36 N (8lbs), or greater than about 44 N (10 lbs).

Embodiment DD69 is the method of any one of embodiments DD1 to DD67,wherein the shaped porous carbon product has a mechanical piece crushstrength from about 22 N (5 lbs) to about 88 N (20 lbs), from about 22 N(5 lbs) to about 66 N (15 lbs), or from about 33 N (7.5 lbs) to about 66N (15 lbs).

Embodiment DD70 is the method of any one of embodiments DD1 to DD69,wherein the shaped porous carbon product has a mean diameter of at leastabout 50 μm, at least about 500 μm, at least about 1,000 μm, or at leastabout 10,000 μm.

Embodiment DD71 is the method of any one of embodiments DD1 to DD70,wherein the shaped porous carbon product has the carbon black content ofat least about 35 wt. %, at least about 40 wt. %, at least about 45 wt.%, at least about 50 wt. %, at least about 55 wt. %, at least about 60wt. %, at least about 65 wt. %, or at least about 70 wt. %.

Embodiment DD72 is the method of any one of embodiments DD1 to DD70,wherein the shaped porous carbon product has the carbon black contentfrom about 35 wt. % to about 80 wt. %, from about 35 wt. % to about 75wt. %, from about 40 wt. % to about 80 wt. %, or from about 40 wt. % toabout 75 wt. %.

Embodiment DD73 is the method of any one of embodiments DD1 to DD72,wherein the shaped porous carbon product has a carbonized binder contentfrom about 10 wt. % to about 50 wt. %, from about 20 wt. % to about 50wt. %, from about 25 wt. % to about 40 wt. %, or from about 25 wt. % toabout 35 wt. %.

Embodiment DD74 is the method of any one of embodiments DD1 to DD73,wherein the catalyst composition exhibits a rotating drum attritionindex as measured in accordance with ASTM D4058-96 such that the percentretained is greater than about 85%, greater than about 90%, greater thanabout 92%, or greater than about 95%.

Embodiment DD75 is the method of any one of embodiments DD1 to DD73,wherein the catalyst composition exhibits a rotating drum attritionindex as measured in accordance with ASTM D4058-96 such that the percentretained is greater than about 97%, or greater than about 99% by weight.

Embodiment DD76 is the method of any one of embodiments DD1 to DD75,wherein the catalyst composition exhibits a horizontal agitation sieveabrasion loss of less than about 5%, or less than about 3%.

Embodiment DD77 is the method of any one of embodiments DD1 to DD75,wherein the catalyst composition exhibits a horizontal agitation sieveabrasion loss of less than about 2%, less than about 1%, less than about0.5%, less than about 0.2%, less than about 0.1%, less than about 0.05%,or less than about 0.03% by weight.

Embodiment EE1 is a method of preparing a catalyst composition, themethod comprising depositing a catalytically active component orprecursor thereof at a surface of the shaped porous carbon product ofany one of embodiments AA1 to AA51 as a catalyst support.

Embodiment EE2 is the method of embodiment EE1, wherein thecatalytically active component or precursor thereof comprises a metal.

Embodiment EE3 is the method of embodiment EE2, wherein the metalcomprises at least one d-block metal.

Embodiment EE4 is the method of embodiment EE2, wherein the metalcomprises at least one metal selected from groups VI, V, VI, VII, VIII,IX, X, XI, XII, and XIII.

Embodiment EE5 is the method of embodiment EE2, wherein the metal isselected from the group consisting of cobalt, nickel, copper, zinc,iron, vanadium, molybdenum, manganese, barium, ruthenium, rhodium,rhenium, palladium, silver, osmium, iridium, platinum, gold, andcombinations thereof.

Embodiment FF1 is a process for the selective oxidation of an aldose toan aldaric acid comprising reacting the aldose with oxygen in thepresence of a catalyst composition prepared according to any one ofembodiments EE1 to EE5 to form the aldaric acid.

Embodiment FF2 is the process of embodiment FF1, wherein the aldose isselected from the group consisting of pentoses and hexoses.

Embodiment FF3 is the process of embodiment FF1 or FF2, wherein thealdaric acid is selected from the group consisting of xylaric acid andglucaric acid.

Embodiment FF4 is the process of any one of embodiments FF1 to FF3,wherein the catalytically active component of the catalyst compositioncomprises at least platinum.

Embodiment FF5 is the process of any one of embodiments FF1 to FF4,wherein the catalytically active component of the catalyst compositioncomprises platinum and gold.

Embodiment FF6 is the process of any one of embodiments FF1 to FF5,wherein the aldaric acid comprises glucaric acid and the glucaric acidyield is at least about 30%, at least about 35%, at least about 40%, atleast about, 45%, or at least about 50%.

Embodiment FF7 is the process of any one of embodiments FF1 to FF5,wherein the aldaric acid comprises glucaric acid and the glucaric acidyield is from about 35% to about 65%, from about 40% to about 65%, orfrom about 45% to about 65%.

Embodiment FF8 is the process of any one of embodiments FF1 to FF7,wherein the aldaric acid comprises glucaric acid and the glucaric acidselectivity is at least about 70%, at least about 75%, or at least about80%.

Embodiment FF9 is the process of any one of embodiments FF1 to FF8,wherein the aldose comprises glucose and the catalytically activecomponent comprises platinum and the mass ratio of glucose to platinumis from about 10:1 to about 1000:1, from about 10:1 to about 500:1, fromabout 10:1 to about 200:1, or from about 10:1 to about 100:1.

Embodiment GG1 is a process for the selective hydrodeoxygenation ofaldaric acid or salt, ester, or lactone thereof to a dicarboxylic acidcomprising reacting the aldaric acid or salt, ester, or lactone thereofwith hydrogen in the presence of a halogen-containing compound and acatalyst composition prepared according to of any one of embodiments EE1to EE5 to form the dicarboxylic acid.

Embodiment GG2 is the process of embodiment GG1, wherein the aldaricacid or salt, ester, or lactone thereof comprises glucaric acid or salt,ester, or lactone thereof.

Embodiment GG3 is the process of embodiment GG1 or GG2, wherein thedicarboxylic acid comprises adipic acid.

Embodiment GG4 is the process of any one of embodiments GG1 to GG3,wherein the catalytically active component of the catalyst compositioncomprises at least one noble metal.

Embodiment HH1 is a process for the selective hydrodeoxygenation of1,2,6-hexanetriol to 1,6-hexanediol comprising reacting the1,2,6-hexanetriol with hydrogen in the presence of a catalystcomposition prepared according to of any one of embodiments EE1 to EE5to form 1,6-hexanediol.

Embodiment HH2 is the process of embodiment HH1, wherein thecatalytically active component comprises platinum and at least one metalselected from the group consisting of molybdenum, lanthanum, samarium,yttrium, tungsten, and rhenium at a surface of the support.

Embodiment HH3 is the process of embodiment HH1 or HH2, wherein thecatalytically active component of the catalyst composition comprisesplatinum and tungsten.

Embodiment HH4 is the process of any one of embodiments HH1 to HH3,wherein the total metal loading of the catalyst composition is fromabout 0.1% to about 10%, or from 0.2% to 10%, or from about 0.2% toabout 8%, or from about 0.2% to about 5%, of the total weight of thecatalyst.

Embodiment HH5 is the process of any one of embodiments HH1 to HH4,wherein the molar ratio of platinum to M2 metal is from about 20:1 toabout 1:10, from about 10:1 to about 1:5, or from about 8:1 to about1:2.

Embodiment HH6 is the process of any one of embodiments HH1 to HH4,wherein the reaction of 1,2,6-hexanetriol to 1,6-hexanediol is conductedat a temperature in the range of about 60° C. to about 200° C. or about120° C. to about 180° C. and a partial pressure of hydrogen in the rangeof about 200 psig to about 2000 psig or about 500 psig to about 2000psig.

Embodiment II1 is a process for the selective amination of1,6-hexanediol to 1,6-hexamethylenediamine comprising reacting the1,6-hexanediol with an amine in the presence of a catalyst compositionprepared according to of any one of embodiments EE1 to EE5 to form1,6-hexamethylenediamine.

Embodiment II2 is the process of embodiment II1, wherein the aminecomprises ammonia.

Embodiment II3 is the process of embodiment II2, wherein the molar ratioof ammonia to 1,6-hexanediol is at least about 40:1, at least about30:1, at least about 20:1, or in the range of from about 40:1 to about5:1, or from about 30:1 to about 10:1.

Embodiment II4 is the process of any one of embodiments II1 to II3,wherein the reaction of 1,6-hexanediol with amine in the presence of thecatalyst composition is carried out at a temperature less than or equalto about 200° C., less than or equal to about 100° C., or in the rangeof about 100° C. to about 180° C., or about 140° C. to about 180° C.

Embodiment II5 is the process of any one of embodiments II1 to II4,wherein the reaction of 1,6-hexanediol with amine in the presence of thecatalyst composition is conducted at a pressure not exceeding about 1500psig, in the range of about 200 psig to about 1500 psig, of about 400psig to about 1200 psig, of about 400 psig to about 1000 psig.

Embodiment II6 is the process of any one of embodiments II1 to II5,wherein the reaction of 1,6-hexanediol with amine in the presence of thecatalyst composition is conducted with 1,6-hexanediol and ammonia at atemperature in the range of about 100° C. to about 180° C. and apressure in the range of about 200 psig to about 1500 psig.

Embodiment II7 is the process of any one of embodiments II1 to II6,wherein the 1,6-hexanediol and amine are reacted in the presence ofhydrogen and the catalyst composition, and the hydrogen partial pressureis equal to or less than about 100 psig.

Embodiment II8 is the process of any one of embodiments II1 to II7,wherein at least 20%, at least 30%, at least 40%, at least 50%, at least60%, or at least 70% of the product mixture resulting from a single passreaction of 1,6-hexanediol with amine (e.g., ammonia) in the presence ofthe catalyst composition is 1,6-hexamethylenediamine.

Embodiment II9 is the process of any one of embodiments II1 to II8wherein the catalytically active component comprises ruthenium.

Embodiment II10 is the process of any one of embodiments II1 to II9wherein the catalytically active component comprises rhenium.

Embodiment II11 is the process of any one of embodiments II1 to II10,wherein the total metal loading of the catalyst composition is fromabout 0.1% to about 10%, from about 1% to about 6%, or from about 1% toabout 5% of the total weight of the catalyst.

Embodiment II12 is the process of any one of embodiments II1 to II11,wherein the catalytically active component of the catalyst compositionfurther comprises rhenium and the molar ratio of ruthenium:rhenium isfrom about 20:1 to about 4:1, from about 10:1 to about 4:1, or fromabout 8:1 to about 4:1.

Embodiment II13 is the process of any one of embodiments Ill to 1112,wherein the catalytically active component of the catalyst compositioncomprises nickel.

For further illustration, additional non-limiting embodiments of thepresent disclosure are set forth below.

The following non-limiting examples are provided to further illustratethe present invention.

EXAMPLES

Surface areas were determined from nitrogen adsorption data using theBET method as described in S. Brunauer, P. H. Emmett, E. Teller, J. Am.Chem. Soc. 1938, 60, 309-331, and ASTM D3663-03(2008) Standard TestMethod for Surface Area of Catalysts and Catalyst Carriers. Mean porediameters and pore volumes were determined in accordance with theprocedures described in E. P. Barrett, L. G. Joyner, P. P. Halenda, J.Am. Chem. Soc. 1951, 73, 373-380, and ASTM D4222-03(2008) Standard TestMethod for Determination of Nitrogen Adsorption and Desorption Isothermsof Catalysts and Catalyst Carriers by Static Volumetric Measurements.

Mercury Porosimetry measurements were conducted using an AutoPore VMercury Porosimeter from Micromeritics Instrument Corporation. Asuitable amount of carbon extrudates were loaded into an appropriatepenetrometer and mercury intrusion was measured in two sequentialstages: low pressure analysis (0 to 50 psia) followed by high pressureanalysis (50 to 33,000 psia). A total of 712 data points were collectedacross the whole range of pressure with a contact angle of 154.0°.

Radial piece crush strength measurements were conducted according toASTM D6175-03(2013) Standard Test Method for Radial Crush Strength ofExtruded Catalyst and Catalyst Carrier Particles using a press apparatusequipped with a Dillon GS100 Digital Force Gauge. Mean radial piececrush strength is the average value of independent measurements of atleast 10 different extrudate pellets.

Single piece crush strength were conducted according to ASTMD4179-03(2013) Standard Test Method for Single Pellet Crush Strength ofFormed Catalysts and Catalyst Carriers using a press apparatus equippedwith a Dillon GS100 Digital Force Gauge. Single piece crush strength isthe average value of independent measurements of at least 10 differentextrudate pellets.

Example 1. Preparation of Carbon Black Extrudates

36.4 g of carbon black powder (Cabot Vulcan XC72, 224 m²/g) was added inmultiple portions to a heated (overnight at 80° C.) aqueous solution(136.5 g) containing 24.3 wt. % Cerelose Dextrose from Ingredion and 4.7wt. % hydroxyethylcellulose from Sigma-Aldrich (SKU 54290, viscosity80-125 cP, 2% in H₂O (20° C.)). The mixture was stirred well using aspatula to produce a paste. This paste was loaded into a syringe and thematerial was extrudated into spaghetti-like strings with about 1.5 mmdiameter. After drying in a 70° C. oven for 5 hours under a dry airpurge, these strings were cut into small pieces about 1.0 cm long. Thenthey were treated at 350° C. for 2 hours with 10° C./min temperatureramp rate under continuous N₂ flow to carbonize the binder and produce acarbon black extrudate.

The properties of the resultant extrudate are show in Table 1.

TABLE 1 BET Mean Surface Pore Pore Area Diameter Volume (m²/g) (Å)(cm³/g) Extrudate of 110 110 0.15 Cabot Vulcan XC72

Example 2. Characterization of Component Carbon Black Powder

The properties of various carbon black powders utilized in the shapedporous carbon black products were characterized.

A. Physical Properties of Carbon Black Powders

The BET specific surface area, specific mean pore diameter and specificpore volume of these carbon black powder starting materials weredetermined using the methods described above, and are provided in Table2.

TABLE 2 BET Mean Surface Pore Pore Area Diameter Volume Carbon Black(m²/g) (Å) (cm³/g) Asbury 5365R 34 143 0.11 Asbury 5353R 35 186 0.14Asbury 5345R 35 207 0.11 Timcal Ensaco 250G 64 140 0.24 Asbury 5348R 65220 0.31 Asbury 5358R 67 213 0.34 Asbury 5346R 80 145 0.28 Cabot Monarch570 102 138 0.30 Orion HP 160 158 208 0.87 Cabot Monarch 700 181 1210.38 Cabot Vulcan XC72 224 161 0.43

B. Catalytic Performance

The carbon black powders were evaluated as catalyst support material inan oxidation reaction for converting glucose to glucaric acid asdescribed below.

(i) Oxidation of Glucose to Glucaric Acid (Protocol 1)

Suitably concentrated aqueous solutions of Me₄NAuO₂ and PtO(NO₃) wereadded together to carbon black powders by incipient wetness impregnationand agitated to impregnate the supports. The samples were dried in anoven at 70° C. overnight, and reduced at 350° C. under a forming gas (5%H₂ and 95% N₂) atmosphere for 4 hours with 2° C./min temperature ramprate to produce catalysts with a composition of 2.0 wt % Au and 2.0 wt %Pt. By using other carbon black supports, Au and Pt precursors, andadjusting amount of Au and Pt in solution, different catalysts withvarious Au and Pt loadings on a variety of commercial carbon blackpowders or particles from extrudates were prepared in a similar manner.

These catalysts were tested for glucose oxidation using the followingtesting protocol. Catalyst (8 mg) was weighed into a glass vial insertfollowed by addition of an aqueous glucose solution (250 μl of 0.55 M).The glass vial insert was loaded into a reactor and the reactor wasclosed. The atmosphere in the reactor was replaced with oxygen andpressurized to 75 psig at room temperature. Reactor was heated to 110°C. and maintained at the respective temperature for 2 hours while vialswere shaken. After that, shaking was stopped and reactor was cooled to40° C. Pressure in the reactor was then slowly released. The glass vialinsert was removed from the reactor and centrifuged. The solution wasdiluted with deionized water and analyzed by ion chromatography todetermine the yield of glucaric acid. Selectivity is defined as100%×(glucaric acid)/(sum of glucaric acid and all off-pathway species).Off-pathway species that cannot be converted to glucaric acid include2-ketogluconic acid, 3-ketogluconic acid, 4-ketogluconic acid,5-ketogluconic acid, trihydroxyglutaric acid, tartaric acid, tartronicacid and oxalic acid. On-pathway species include glucose, gluconic acid,guluronic acid and glucuronic acid. On-pathway species are not used inthe selectivity calculation because these intermediates can be partiallyconverted to glucaric acid and are not considered off-pathway. Resultsare presented in Table 3.

TABLE 3 Mean Glucaric Surface Pore Pore Acid Select- Area DiameterVolume Yield ivity Support (m²/g) (Å) (cm³/g) (%) (%) Asbury 5302 211 990.29 33 76 Asbury 5303 219 79 0.23 38 77 Asbury 5368 303 102 0.54 34 78Asbury 5379 271 163 0.83 33 75

(ii) Oxidation of Glucose to Glucaric Acid (Protocol 2)

Suitably concentrated aqueous solutions of K₂Pt(OH)₆ and CsAuO₂ wereadded together to carbon black powders by incipient wetness impregnationand agitated to impregnate the supports. The samples were dried in anoven at 40° C. overnight, and reduced at 250° C. under a forming gas (5%H₂ and 95% N₂) atmosphere for 3 hours with 5° C./min temperature ramprate. The final catalysts were washed with deionized water and finallydried at 40° C. to produce catalysts with a composition of 2.44 wt. % Ptand 2.38 wt. % Au. By using other carbon black supports, Au and Ptprecursors, and adjusting amount of Au and Pt in solution, differentcatalysts with various Au and Pt loadings on a variety of commercialcarbon black powders or particles from extrudates were prepared in asimilar manner.

These catalysts were tested for glucose oxidation using the followingtesting protocol. Catalyst (10 mg) was weighed into a glass vial insertfollowed by addition of an aqueous glucose solution (250 μl of 0.55 M).The glass vial insert was loaded into a reactor and the reactor wasclosed. The atmosphere in the reactor was replaced with oxygen andpressurized to 75 psig at room temperature. Reactor was heated to 90° C.and maintained at the respective temperature for 5 hours while vialswere shaken. After that, shaking was stopped and reactor was cooled to40° C. Pressure in the reactor was then slowly released. The glass vialinsert was removed from the reactor and centrifuged. The solution wasdiluted with deionized water and analyzed by ion chromatography todetermine the yield of glucaric acid and the selectivity as definedherein. Results are presented in Table 4.

TABLE 4 Mean Glucaric Surface Pore Pore Acid Select- Area DiameterVolume Yield ivity Support (m²/g) (Å) (cm³/g) (%) (%) Asbury 5365R 34143 0.11 42 78 Asbury 5353R 35 186 0.14 38 82 Asbury 5345R 35 207 0.1144 76 Timcal Ensaco 250G 64 140 0.24 60 83 Asbury 5348R 65 220 0.31 5478 Asbury 5358R 67 213 0.34 52 77 Asbury 5346R 80 145 0.28 48 75 CabotMonarch 570 102 138 0.3 37 75 Orion HP 160 158 208 0.87 35 77 CabotMonarch 700 181 121 0.38 42 77 Cabot Vulcan XC72 224 161 0.43 46 77

Example 3. Preparation of Shaped Porous Carbon Black Product Using aVariety of Carbon Black Powders and Binders

By using other carbon black powders and carbohydrate binders, differentcarbon black extrudates were prepared as described in Example 1. Othercarbon black powders included, but were not limited to, Orion carbonHI-BLACK 40B2, Orion HI-BLACK 50LB, Orion Hi-Black SOL, Orion HP-160,Orion Carbon HI-BLACK N330, Timcal Ensaco 150 G, Timcal Ensaco 250 G,Timcal Ensaco 260G, Timcal Ensaco 250P, Cabot Vulcan XC72R, CabotMonarch 120, Cabot Monarch 280, Cabot Monarch 570, Cabot Monarch 700,Asbury 5365R, Asbury 5353R, Asbury 5345R, Asbury 5352, Asbury 5374,Asbury 5348R, Asbury 5358R, Sid Richardson SC159, Sid Richardson SR155.Other carbohydrate binders included, but were not limited to, CargillClearbrew 60/44 IX (80% Carbohydrate), Casco Lab Fructose 90 (70%Carbohydrate) and Molasses (80% Carbohydrate). Formulations with thesevariations yielded illustrative examples of the shaped carbon product ofthe present invention. The properties of some of these embodiments aredescribed in more detail below.

Example 4. Crush Testing of Carbon Black Extrudates

Extrudate pellets (Nos. 1-8 below), having an approximately 1.5 mmdiameter, were prepared according to the method described in Example 1except that the final pyrolysis times and temperatures were varied aslisted in Table 5 in the extrudate description column. After thepyrolysis step the extrudates were cut to the sizes ranging from 2-6 mmin length. The percentage of carbonized binder (after pyrolysis) presentin the shaped carbon product was determined by mass balance [i.e.,[(Weight_(Shaped Carbon Product)−Weight_(Carbon Black (in formulation))/Weight_(Shaped Carbon Product))×100].Total binder content after pyrolysis (i.e., total carbonized binder)varied from 15-50 wt. %.

Additional extrudate pellets (Nos. 9-11 below) were prepared accordinglyto the following procedure. Approximately 24.0 g of carbon black powder(Timcal Ensaco 250G, 65 m²/g) was added in multiple portions to anaqueous solution (100.0 g) containing 25.0 wt. % Cerelose Dextrose fromIngredion. The mixture was stirred well using a spatula to produce apaste. This paste was loaded into a syringe and the material wasextrudated into spaghetti-like strings with a 1.5 mm diameter. Afterdrying in a 100° C. oven for 3 hours under a dry air purge, thesestrings were cut into smaller pieces (2-6 mm lengths). Then they weretreated at one of the following conditions to produce carbon blackextrudates: (1) 250° C. for 3 hours with 10° C./min temperature ramprate under continuous N₂ flow; (2) 800° C. for 4 hours with 10° C./mintemperature ramp rate under continuous N₂ flow; (3) 200° C. for 3 hourswith 10° C./min temperature ramp rate in air. Binder content varied from15 to 50 wt. %. Table 5 presents the crush strength data for theextrudates prepared.

TABLE 5 Mean Mean Radial Mean Radial Carbonized Mechanical Piece CrushPiece Crush Binder Piece Crush Strength Strength Content No. ExtrudateDescription Strength (lb) (N/mm) (lb/mm) (wt. %) 1 Cabot Monarch 120 8.79.2 2.1 15 (Glucose + Hydroxyethylcellulose binder, 350° C./2 h/N₂) 2Cabot Monarch 280 5.4 7.7 1.7 23 (Glucose + Hydroxyethylcellulosebinder, 800° C./2 h/N₂) 3 Cabot Monarch 700 12.3 12.3 2.8 31 (Glucose +Hydroxyethylcellulose binder, 350° C./2 h/N₂) 4 Cabot Monarch 700 6.36.3 1.4 34 (Glucose + Hydroxyethylcellulose binder, 500° C./2 h/N₂) 5Cabot Monarch 700 18.7 18.5 4.2 31 (Glucose + Hydroxyethylcellulosebinder, 800° C./2 h/N₂) 6 Cabot Vulcan XC72 5.6 5.6 1.2 30 (Glucose +Hydroxyethylcellulose binder, 800° C./2 h/N₂) 7 Cabot Vulcan XC72R 7.87.8 1.8 38 (Glucose + Hydroxyethylcellulose binder, 350° C./2 h/N₂) 8Timcal Ensaco 250P 8.6 8.6 1.9 50 (Glucose + Hydroxyethylcellulosebinder, 350° C./2 h/N₂) 9 Timcal Ensaco 250G 10.9 10.9 2.5 32 (Glucosebinder, 800° C./4 h/N₂) 10 Timcal Ensaco 250G 6.2 6.2 1.4 29 (Glucosebinder, 200° C./3 h/Air) 11 Timcal Ensaco 250G 3.8 3.8 0.9 29 (Glucosebinder, 250° C./3 h/N₂)

Example 5. Preparation of Catalyst Compositions

The Cabot Vulcan XC72 carbon black extrudates prepared in Example 1 werefurther cut into small pieces of about 0.5 cm long for testing. Anaqueous solution (13 ml) containing 0.17 g Au in the form of Me₄NAuO₂and 0.26 g Pt in the form of PtO(NO₃) was mixed with 21.5 g of theseextrudates. The mixture was agitated to impregnate the carbon blacksupport and was dried in a 60° C. oven overnight under a dry air purge.The sample was then reduced at 350° C. under forming gas (5% H₂ and 95%N₂) atmosphere for 4 hours with 2° C./min temperature ramp rate. Thefinal catalyst was composed of about 0.80 wt. % Au and 1.2 wt. % Pt.

By using other carbon black extrudates prepared from the methoddescribed above, a series of Pt—Au extrudate catalysts spanning rangesin Au and Pt loadings, Pt/Au ratios and metal distributions (e.g.,eggshell, uniform, subsurface bands) could be prepared.

The cross section of a sample of the catalyst extrudate prepared withCabot Vulcan XC72 carbon black was analyzed using scanning electronmicroscopy. FIG. 1 provides an image of this analysis. The image showsthat platinum and gold metal was deposited on the external surface ofthe carbon black extrudate forming a shell coating the outer surfacesthe carbon black extrudate. FIG. 2 provides a magnified view of one ofcatalyst extrudate cross-sections with measurements of the diameter ofthe carbon black extrudate (i.e., 1.14 mm) and thickness of the platinumand gold shell (average of about 100 μm) on the carbon black extrudateouter surface.

Example 6. Testing of Au/Pt Carbon Black Extrudate Catalysts (UsingCabot Monarch 700) in a Fixed-Bed Reactor for the Oxidation of Glucoseto Glucaric Acid

Extrudates based on carbon black Cabot Monarch 700 with glucose andhydroxyethylcellulose binder and subsequent catalyst with 0.80 wt. % Auand 1.20 wt. % Pt were prepared by mixing carbon black Cabot Monarch 700(42.0 g) and a binder solution (145.8 g prepared by heating a solutioncontaining 3.4 wt % hydroxyethylcellulose and 28.6 wt % glucose at 80°C. overnight)), The resultant paste was loaded into a syringe and thematerial was extrudated into spaghetti-like strings with a 1.5 mmdiameter. After drying in a 100° C. oven for 3 hours under a dry airpurge, these strings were cut into smaller pieces (2-6 mm lengths) andpyrolyzed at 350° C. for 2 hours under a nitrogen atmosphere. The finalcarbonized binder content in carbon extrudates was 31 wt %. The catalystwas then prepared using the method described in Example 5. Oxidation ofglucose reactions were conducted in a 12.7 mm (0.5-inch) OD by 83 cmlong 316 stainless steel tube with co-current down-flow of gas andliquid. Catalyst beds were vibration packed with 1.0 mm glass beads atthe top to approximately 8 cm depth, followed by catalyst (67 cm beddepth containing 20.0 g, 0.80 wt. % Au+1.2 wt. % Pt on Cabot Monarch 700carbon black pellets with a length of 0.5 cm and diameter of 1.5 mmprepared using the method described in Example 3), then 1.0 mm glassbeads at the bottom to approximately 8 cm depth. Quartz wool plugsseparated the catalyst bed from the glass beads.

The packed reactor tube was clamped in an aluminum block heater equippedwith PID controller. Gas (compressed dry air) and liquid flows wereregulated by mass flow controller and HPLC pump, respectively. A backpressure regulator controlled reactor pressure as indicated in Table 6.The catalyst was tested for approximately 350 hours of time on stream(TOS).

Table 6 describes the fixed bed reactor conditions and resultantextrudate catalyst performance. The catalyst productivity in Table 6 is35 gram (glucaric acid) per gram (Pt+Au)⁻¹ hr⁻¹ or 0.70 gram (glucaricacid) per gram (catalyst)⁻¹ hr⁻¹.

TABLE 6 Gas Reactor block Glucose feed Reactor Liquid flowrate/ Glucarictemperature/ concentration/ pressure/ flowrate/ mL min⁻¹ Glucose acid °C. wt. % psi mL min⁻¹ (STP) conversion/% yield/% Selectivity/% 130 20750 2.00 768 >99 50 86

BET surface area measurements and BJM pore volume distributionmeasurements were made on the following carbon black and extrudatesamples:

Sample 1: Monarch 700 carbon black material.

Sample 2: Fresh Monarch 700 extrudate prepared in accordance with thisExample.

Sample 3: Monarch 700 extrudate of Example 4 following 350 hours onstream in a fixed bed reactor (described in Example 6).

Sample 4: An aqueous solution (915.0 g) containing 4.0 wt %hydroxyethylcellulose (Sigma-Aldrich, SKU 54290, viscosity 80-125 cP, 2%in H₂O (20° C.)) and 56.0 wt % glucose (ADM Corn Processing, DextroseMonohydrate 99.7DE with 91.2255 wt % Glucose content) was prepared bystirring 36.6 g hydroxyethylcellulose and 561.7 g Dextrose Monohydratein 316.7 ml D.I. water at 80° C. for 16 hours. After cooling to ambienttemperature, this viscous solution was added to 400.0 g carbon blackpowder (Cabot Monarch 700) in a blender/kneader and the material wasmixed/kneaded for 1 hour. The material was then loaded into a 1″ BonnotBB Gun Extruder and extrudated into spaghetti like strings with ca. 1.5mm diameter at cross section. These strings were dried under a dry airpurge in a 120° C. oven for 16 hours and then pyrolyzed at 800° C. for 2hours with 5° C./min ramp rate under a nitrogen purge. The finalcarbonized binder content was to be 36 wt %.

Sample 5: Prepared as described by Example 9.

Sample 6: Prepared as described by Example 12.

Sample 7: An aqueous solution (166.0 g) containing 4.0 wt %hydroxyethylcellulose (Sigma-Aldrich, SKU 54290, viscosity 80-125 cP, 2%in H₂O (20° C.)) and 56.0 wt % glucose (ADM Corn Processing, DextroseMonohydrate 99.7DE with 91.2255 wt % Glucose content) was prepared bystirring 6.64 g hydroxyethylcellulose and 84.8 g Dextrose Monohydrate in74.6 ml D.I. water at 80° C. for 16 hours. After cooling to ambienttemperature, this viscous solution was added to 60.0 g carbon powder(Asbury 5368) in a blender/kneader and the material was mixed/kneadedfor 1 hour. The material was then loaded into a 1″ Bonnot BB GunExtruder and extrudated into spaghetti like strings with ca. 1.5 mmdiameter at cross section. These strings were dried under a dry airpurge in a 120° C. oven for 16 hours and then pyrolyzed at 800° C. for 2hours with 5° C./min ramp rate under a nitrogen purge. The finalcarbonized binder content was 40 wt %.

Sample 8: Commercially available activated carbon extrudate Süd ChemieG32H-N-75.

Sample 9: Commercially available activated carbon extrudate DonauSupersorbon K4-35.

The results are presented in Table 7.

TABLE 7 Pores Pores BET between 10 between 10 Carbonized Surface MeanPore BJH Pore Pores < 3 nm and 50 nm and 100 nm Binder Area DiameterVolume (% of BJH (% of BJH (% of BJH Content Sample (m²/g) (nm) (cm³/g)pore volume) pore volume) pore volume) (wt %) Sample 1 180 12 0.38 5 4075 0 Sample 2 178 11 0.29 7 45 75 36 Sample 3 98 18 0.31 3 50 90 36Sample 4 182 13 0.36 4 55 80 36 Sample 5 194 11 0.29 6 45 75 36 Sample 5234 10 0.29 7 45 70 36 Sample 6 218 12 0.33 5 60 80 40 Sample 8 1164 3.40.63 40 <15 15 ** Sample 9 1019 2.7 0.31 65 5 7 **

FIG. 3 presents a plot of the cumulative pore volume (%) as a functionof mean pore diameter for a raw Monarch 700 carbon black material. FIG.4 presents a plot of the cumulative pore volume (%) as a function ofmean pore diameter for a fresh catalyst prepared from a carbon blackextrudate using Monarch 700 and a glucose/hydroxyethylcellulose binder.FIG. 5 presents a plot of the cumulative pore volume (%) as a functionof mean pore diameter for the catalyst extrudate of FIG. 2 following 350hours of use in a fixed bed reactor for the oxidation of glucose toglucaric acid. FIG. 6 presents a plot of the cumulative pore volume (%)as a function of mean pore diameter for a extrudate using Monarch 700carbon black and a glucose/hydroxyethyl cellulose binder. FIG. 7presents a plot of the cumulative pore volume (%) as a function of meanpore diameter for a extrudate using Sid Richardson SC 159 carbon blackand a glucose/hydroxyethyl cellulose binder. FIG. 8 presents a plot ofthe cumulative pore volume (%) as a function of mean pore diameter for aextrudate using Sid Richardson SC 159 carbon black and aglucose/hydroxyethyl cellulose binder prepared in accordance withExample 12. FIG. 9 presents a plot of the cumulative pore volume (%) asa function of mean pore diameter for a extrudate using Asbury 5368carbon black and a glucose/hydroxyethyl cellulose binder. FIG. 10presents a plot of the cumulative pore volume (%) as a function of meanpore diameter for a commercially available activated carbon extrudate ofSüd Chemie G32H-N-75. FIG. 11 presents a plot of the cumulative porevolume (%) as a function of mean pore diameter for a commerciallyavailable activated carbon extrudate of Donau Supersorbon K4-35.

FIG. 12 presents the pore size distribution for an extrudate using SidRichardson SC159 carbon black and a glucose/hydroxyethyl cellulosebinder measured by mercury porosimetry. These plots show that themicropore contribution to pore volume for carbon black extrudatecatalysts (fresh and after use) is very low. In particular the plotsshow that the micropore contribution (pores <3 nm) is less than 10% ofthe BJH pore volume. In some instances the micropore contribution (pores<3 nm) is less than 6% of the BJH pore volume, and in some instances themicropore contribution (pores <3 nm) is less than 4% of the BJH porevolume. In contrast, the micropore contribution to pore volume for anactivated carbon extrudate catalyst is exceedingly high at 40%. Also,the plots show that the contribution to pore volume from pores having amean diameter from about 10 nm to 50 nm for the carbon black catalystswas about 40% or higher. On the other hand, the contribution to porevolume from pores having a mean diameter from about 10 nm to 50 nm forthe activated carbon catalyst was less than 15%. The plots show that thecontribution to pore volume from pores having a mean diameter from about10 nm to 100 nm for the carbon black catalysts was about 70% or higher.On the other hand, the contribution to pore volume from pores having amean diameter from about 10 nm to 100 nm for the activated carboncatalyst was 15% or less.

Example 7. Testing of Au/Pt Carbon Black Extrudate Catalysts (UsingCabot Vulcan XC72) in a Fixed-Bed Reactor for the Oxidation of Glucoseto Glucaric Acid

Extrudates based on carbon black Cabot Vulcan XC72 and subsequentcatalyst with 0.80 wt. % Au and 1.20 wt. % Pt were prepared by mixingcarbon black Cabot Vulcan XC72 (36.4 g) and a binder solution (136.5 gprepared by heating a solution containing 3.7 wt % hydroxyethylcelluloseand 24.4 wt % glucose at 80° C. overnight). The resultant paste wasloaded into a syringe and the material was extrudated intospaghetti-like strings with a 1.5 mm diameter followed by drying at 120°C. for 4 hours in air, and pyrolysis at 350° C. for 2 hours under anitrogen atmosphere. The final binder content in pyrolyzed carbonextrudates was 30 wt %. The catalysts were prepared using the methoddescribed in Example 3. The catalyst was tested in the same 12.7 mm(0.5-inch) OD fixed-bed reactor as in Example 6. Table 8 describes thefixed bed reactor conditions and resultant extrudate catalystperformance. The catalyst productivity in Table 8 is 36 gram (glucaricacid) per gram (Pt+Au)⁻¹ hr⁻¹ or 0.72 gram (glucaric acid) per gram(catalyst)⁻¹ hr⁻¹.

TABLE 8 Gas Reactor block Glucose feed Reactor Liquid flowrate/ Glucarictemperature/ concentration/ pressure/ flowrate/ mL min⁻¹ Glucose acid °C. wt. % psi mL min⁻¹ (STP) conversion/% yield/% Selectivity/% 130 20750 2.00 768 >99 52 87

Example 8. Oxidation of Glucose to Glucaric Acid—Activated Carbons withHigh Surface Areas (Comparative)

The same synthesis procedure described in Example 6 was used to preparePt—Au catalysts supported on high surface area activated carbon. Theactivated carbon extrudates were crushed and sieved to <90 μm prior tothe catalyst preparation and screening. The catalysts were screened inthe same reactor under the same conditions described in Example2(B)(ii). As shown in Table 9, the high surface area activated carboncarriers were found to exhibit lower activity and lower selectivity (asdefined herein).

TABLE 9 Mean Glucaric Surface Pore Pore Acid Select- Area DiameterVolume Yield ivity Support (m²/g) (Å) (cm³/g) (%) (%) Donau SupersorbonK4-35 1019 27 0.31 22 66 Donau Supersorbon SX30 1050 39 0.71 18 68 NoritRX3 Extra 1239 37 0.23 20 70

Example 9. Preparation of Carbon Black Extrudate Catalysts—Attrition andAbrasion Testing

An aqueous solution (113 g) containing 4.0 wt % hydroxyethylcellulose(Sigma-Aldrich, SKU 54290, viscosity 80-125 cP, 2% in H₂O (20° C.)) and56.0 wt % glucose (ADM Corn Processing, Dextrose Monohydrate 99.7DE with91.2255 wt % Glucose content) was prepared by stirring 4.5 ghydroxyethylcellulose and 69.4 g Dextrose Monohydrate in 39.1 ml D.I.water at 80° C. overnight. After cooling to room temperature, thisviscous solution was added to 50 g carbon black powder (Sid RichardsonSC159, 231 m²/g) in a blender/kneader and the material was mixed/kneadedfor 1 hour. The material was then loaded into a 1″ Bonnot BB GunExtruder and extrudated into spaghetti like strings with ca. 1.5 mmdiameter at cross section. These strings were dried under a dry airpurge in a 120° C. oven overnight and then pyrolyzed at 800° C. for 4hours with 5° C./min ramp rate under a nitrogen purge. The extruded andpyrolyzed samples were cut into small pieces of about 0.5 cm long fortesting.

The properties of the resultant extrudate are show in Table 10. BET andcrush strength measurements performed as described in the currentdisclosure.

TABLE 10 Mean Single Radial BET Mean Piece Piece Surface Pore Pore CrushCrush Area Diameter Volume Strength Strength (m²/g) (Å) (cm³/g) (N)(N/mm) 194 112 0.29 90 30

Extrudates prepared in accordance with this example were tested for thedetermination of attrition index (ASTM D4058-96) and abrasion lossaccording to the procedure described below.

Measurement of Attrition Index.

The ASTM attrition index (ATTR) is a measurement of the resistance of acatalyst or extrudate particle to attrition wear, due to the repeatedstriking of the particle against hard surfaces within the specified testdrum. The diameter and length of the drum is similar to that describedin ASTM D4058, with a rolling apparatus capable of delivering 55 to 65RPM of rotation to the test drum. The percentage of the original samplethat remains on a 20-mesh sieve is called the “Percent Retained” resultof the test. The results of the test can be used, on a relative basis,as a measure of fines production during the handling, transportation,and use of the catalyst or extrudate material. A percent retained resultof >97% is desirable for an industrial application.

Approximately 100 g of the extrudate material prepared in Example 9above was transferred to the test drum which was fastened andtransferred to the rolling apparatus and rolled at 55 to 65 RPM for 35minutes. The weight percent retained after the test was 99.7%.

Measurement of Abrasion Loss.

The abrasion loss (ABL) is an alternate measurement of the resistance ofa catalyst or extrudate particle to wear, due to the intense horizontalagitation of the particles within the confines of a 30-mesh sieve. Theresults of this procedure can be used, on a relative basis, as a measureof fines production during the handling, transportation, and use of thecatalyst or adsorbent material. An abrasion loss of <2 wt % is desiredfor an industrial application. Approximately 100 g of the extrudatematerial prepared in example 9 above was first de-dusted on a 20-meshsieve by gently moving the sieve side-to-side at least 20 times. Thede-dusted sample was then transferred to the inside of a clean, 30-meshsieve stacked above a clean sieve pan for the collection of fines. Thecomplete sieve stack was then assembled onto a RO-Tap RX-29 sieveshaker, covered securely and shaken for 30 minutes. The fines generatedwere weighed to provide a sample abrasion loss of 0.016 wt. %.

Example 10. Testing of Au/Pt Carbon Black Extrudate Catalysts of Example9 in a Fixed-Bed Reactor for the Oxidation of Glucose to Glucaric Acid

The carbon black extrudates prepared from the method described inExample 9 were further cut into small pieces of about 0.5 cm long fortesting. To 27.0 g of these extrudates, an aqueous solution (8.0 ml)containing 0.16 g Au in the form of Me₄NAuO₂ and 0.24 g Pt in the formof PtO(NO₃) was added. The mixture was agitated to impregnate the carbonblack support and was dried in a 70° C. oven for 1 hour under a dry airpurge. The sample was then reduced at 350° C. under forming gas (5% H₂and 95% N₂) atmosphere for 4 hours with 2° C./min temperature ramp rate.The final catalyst was composed of ca. 0.60 wt. % Au and 0.90 wt. % Pt.By using other carbon black extrudates prepared from the methodsdescribed herein, a series of Pt—Au extrudate catalysts spanning rangesin Au and Pt loadings, Pt/Au ratios and metal distributions (e.g.,eggshell, uniform, subsurface bands) can be prepared.

The glucose to glucaric acid oxidation reaction was conducted in a′/2″OD by 83 cm long 316 stainless steel tube with co-current down-flow ofgas and liquid. Catalyst beds were vibration packed with 1.0 mm glassbeads at the top to approximately 10 cm depth, followed by catalyst (63cm bed depth containing 27.4 g, 0.60 wt % Au+0.90 wt % Pt on SidRichardson SC159 carbon black pellets with a length of 0.5 cm anddiameter of 1.4 mm prepared using the method described, then 1.0 mmglass beads at the bottom to approximately 10 cm depth. Quartz woolplugs separated the catalyst bed from the glass beads.

The packed reactor tube was clamped in an aluminum block heater equippedwith PID controller. Gas (compressed dry air) and liquid flows wereregulated by mass flow controller and HPLC pump, respectively. A backpressure regulator controlled reactor pressure as indicated in Table 11.The catalyst was tested for ca. 920 hours on stream and showed stableperformance. Table 11 describes the fixed bed reactor conditions andresultant extrudate catalyst performance. The catalyst productivity inTable 11 is 23 gram (glucaric acid) per gram (Pt+Au)⁻¹ hr⁻¹ or 0.35 gram(glucaric acid) per gram (catalyst)⁻¹ hr⁻¹.

TABLE 11 Gas Reactor block Glucose feed Reactor Liquid flowrate/Glucaric temperature/ concentration/ pressure/ flowrate/ mL min⁻¹Glucose acid ° C. wt % psi mL min⁻¹ (STP) conversion/% yield/%Selectivity/

125 20 750 2.00 512 >99 32 79

indicates data missing or illegible when filed

After 920 hours on stream the catalyst extrudate was removed andre-submitted for mechanical crush strength testing. The mean singlepiece crush strength and mean radial piece crush strength data werefound be within experimental error unchanged from the data listed inTable 10, thereby illustrating that the extrudate catalyst prepared bythe method described is productive, selective and stable under thecontinuous flow conditions described.

Example 11. Testing of Au/Pt Carbon Black Extrudate Catalysts (UsingAsbury 5368) in a Fixed-Bed Reactor for the Oxidation of Glucose toGlucaric Acid

Reactions were conducted in a ½″ OD by 83 cm long 316 stainless steeltube with co-current down-flow of gas and liquid. Catalyst beds werevibration packed with 1.0 mm glass beads at the top to approximately 8cm depth, followed by catalyst (73 cm bed depth containing 35.0 g, 0.50wt % Au+0.85 wt % Pt on Asbury 5368 extruded pellets (as previouslydescribed for Sample 7 (Example 6) with a length of 0.5 cm and diameterof 1.4 mm prepared using the method described in previous example 9),then 1.0 mm glass beads at the bottom to approximately 8 cm depth.Quartz wool plugs separated the catalyst bed from the glass beads.

The packed reactor tube was clamped in an aluminum block heater equippedwith PID controller. Gas (compressed dry air) and liquid flows wereregulated by mass flow controller and HPLC pump, respectively. A backpressure regulator controlled reactor pressure as indicated in Table 12.The catalyst was tested for ca. 240 hours TOS and showed stableperformance. Table 12 describes the fixed bed reactor conditions andresultant extrudate catalyst performance. The catalyst productivity inTable 12 is 20 gram (glucaric acid) per gram (Pt+Au)⁻¹ hr⁻¹ or 0.27 gram(glucaric acid) per gram (catalyst)⁻¹ hr⁻¹.

TABLE 12 0.50 wt % Au + 0.85 wt % Pt/Asbury 5368 Extrudate (stableperformance over 240 hours on stream) Gas Reactor block Glucose feedReactor Liquid flowrate/ Glucaric temperature/ concentration/ pressure/flowrate/ mL min⁻¹ Glucose acid ° C. wt % psi mL min⁻¹ (STP)conversion/% yield/% Selectivity 125 20 750 2.00 512 >99 31 76

Example 12. Preparation of Carbon Black Extrudate Catalysts on PartiallyOxidized Support

Sid Richardson SC159 carbon black extrudates prepared from the methoddescribed in example 9 were oxidized in air at 300° C. for 3 hours with5° C./min ramp rate to give partially oxidized pellets. To 36.0 g ofthese partially oxidized extrudates, an aqueous solution (9.0 ml)containing 0.18 g Au in the form of Me4NAuO2 and 0.31 g Pt in the formof PtO(NO3) was added. The mixture was agitated to impregnate the carbonblack support and was dried in a 60° C. oven overnight under a dry airpurge. The sample was then reduced at 350° C. under forming gas (5% H2and 95% N2) atmosphere for 4 hours with 2° C./min temperature ramp rate.The final catalyst was composed of ca. 0.50 wt % Au and 0.85 wt % Pt. Byusing other carbon black extrudates prepared from the method describedherein, a series of Pt—Au extrudate catalysts spanning ranges in Au andPt loadings, Pt/Au ratios and metal distributions (e.g., eggshell,uniform, subsurface bands) could be prepared. The glucose to glucaricacid oxidation reaction was conducted in a in a′/2″ OD by 83 cm long 316stainless steel tube with co-current down-flow of gas and liquid.Catalyst beds were vibration packed with 1.0 mm glass beads at the topto approximately 6 cm depth, followed by catalyst (70.4 cm bed depthcontaining 34.5 g, 0.50 wt % Au+0.85 wt % Pt on partially oxidized SidRichardson SC159 carbon black pellets with a length of 0.5 cm anddiameter of 1.5 mm prepared using the method described in Example 2),then 1.0 mm glass beads at the bottom to approximately 6 cm depth.Quartz wool plugs separated the catalyst bed from the glass beads.

The packed reactor tube was clamped in an aluminum block heater equippedwith PID controller. Gas (compressed dry air) and liquid flows wereregulated by mass flow controller and HPLC pump, respectively. A backpressure regulator controlled reactor pressure as indicated in Table 13.The catalyst was tested for ca. 230 hours TOS and showed stableperformance. Table 13 describes the fixed bed reactor conditions andresultant extrudate catalyst performance. The catalyst productivity inTable 13 is 26 gram (glucaric acid) per gram (Pt+Au)⁻¹ hr⁻¹ or 0.36 gram(glucaric acid) per gram (catalyst)⁻¹ hr⁻¹.

TABLE 13 Gas Reactor block Glucose feed Reactor Liquid flowrate/Glucaric temperature/ concentration/ pressure/ flowrate/ mL min⁻¹Glucose acid ° C. wt % psi mL min⁻¹ (STP) conversion/% yield/% 125 20750 2.00 512 >99 42

Example 13. Preparation of Carbon Black Extrudates Using aPoly(Vinylalcohol) Porogen

An aqueous solution (490.0 g) containing 8.0 wt % Mowiol 8-88Poly(vinylalcohol) (Mw 67k, Sigma-Aldrich 81383) and 36.0 wt % glucose(ADM Corn Processing, Dextrose Monohydrate 99.7DE with 91.2255 wt %Glucose content) was prepared by stirring 39.2 g Mowiol 8-88Poly(vinylalcohol) and 193.4 g Dextrose Monohydrate in 257.4 ml D.I.water at 70° C. overnight. After cooling to room temperature, thissolution was added to 230 g carbon black powder (Sid Richardson SC159)in a blender/kneader and the material was mixed/kneaded for 1 hour. Thematerial was then loaded into a 1″ Bonnot BB Gun Extruder and extrudatedinto spaghetti like strings with ca. 1.5 mm diameter at cross section.These strings were further dried in a 90° C. oven overnight under a dryair purge and then pyrolyzed at 600° C. for 4 hours with 5° C./min ramprate in a nitrogen atmosphere. The final carbonized binder content was24 wt. %. The resultant extrudate (3-5 mm in length) possessed a surfacearea of 149 m²/g, a pore volume of 0.35 cm³/g and a mean pore diameterof 16 nm. The mean radial piece crush strength of these pellets wasmeasured to be 11.5 N/mm. The single piece crush strength was measuredto be 42N.

Example 14. Testing of Au/Pt Activated Carbon Extrudate Catalysts (UsingClariant Donau Supersorbon K4-35 Activated Carbon Extrudate) in aFixed-Bed Reactor for the Oxidation of Glucose to Glucaric Acid

Catalyst based on activated carbon Clariant Supersorbon K 4-35 wasprepared using the same method described in Example 7. Oxidation ofglucose reactions were conducted using the same method described inExample 2(B)(ii). A catalyst bed depth of 73 cm containing 27.0 g, 0.53wt. % Au+0.90 wt. % Pt on Clariant Supersorbon K 4-35 activated carbonpellets with a length of 0.5 cm and diameter of 1.4 mm was tested forapproximately 40 hours of time on stream (TOS). Table 14 describes thefixed bed reactor conditions and resultant extrudate catalystperformance. After 40 hours on stream the glucaric acid yield and thecatalyst productivity were determined to be lower than the shaped carbonblack catalysts of the invention.

TABLE 14 Reactor Glucose Gas block feed Reactor Liquid flowrate/temperature/ concentration/ pressure/ flowrate/ mL min⁻¹ ° C. wt % psimL min⁻¹ (STP) 125 20 750 2.00 512

Example 15. Preparation of Carbon Black Extrudates

An aqueous solution (915 g) containing 4.0 wt % hydroxyethylcellulose(HEC) (Sigma-Aldrich, SKU 54290, viscosity 80-125 cP at 2% in H₂O (20°C.)) and 56.0 wt % glucose (ADM Corn Processing, Dextrose Monohydrate99.7DE with 91.2 wt % Glucose content) was prepared by stirring 36.6 ghydroxyethylcellulose and 561.7 g Dextrose Monohydrate in 316.7 ml D.I.water at approximately 80° C. for 2 hours. To this viscous solution wasadded 400.1 g of Sid Richardson SC159 carbon black powder, the mixturewas then mixed for a further 10 minutes. The material was then loadedinto a 1″ diameter Bonnot extruder, fitted with a ¼ inch spacer and adie with 1.6 mm cylindrical holes, and extruded into spaghetti-likestrings. The extrudate was dried in a 110° C. oven overnight, thenpyrolyzed in a stationary lab furnace under a nitrogen purge at 800° C.for 4 hours (after ramping the temperature up at 5° C./minute to reachthe target temperature) (Table 15).

TABLE 15 Properties of the pyrolyzed extrudate from Example 15 Radial N₂BET BJH N₂ Diameter Piece Surface Pore at cross Crush Area Volumesection Strength (m²/g) (cm³/g) (mm) (N/mm) 207 0.30 1.5 17

Example 16. Preparation of Carbon Black Extrudates

An aqueous solution (3813 g) containing 4.0 wt % hydroxyethylcellulose(HEC) (Sigma-Aldrich, SKU 54290, viscosity 80-125 cP at 2% in H₂O (20°C.)) and 56.0 wt % glucose (ADM Corn Processing, Dextrose Monohydrate99.7DE with 91.2 wt % Glucose content) was prepared by stirring 153 ghydroxyethylcellulose and 2340 g Dextrose Monohydrate in 1320 ml D.I.water at approximately 80° C. for 3 hours. This viscous solution wasadded over 3.5 minutes to 1670 g of Sid Richardson SC159 carbon blackpowder in a mix-muller, the mixture was then mixed for a further 20minutes in the mix-muller. The material was then loaded into a 2″diameter Bonnot extruder, fitted with 5 dies with 26 cylindrical holeseach 1/16″ internal diameter (JMP Industries, part number 0388P062), andno spacer, and extruded into spaghetti-like strings. 1515 g of theextrudate was dried in a 110° C. oven overnight, to produce 1240 g ofdried extrudate. The product was then pyrolyzed in a stationary tubefurnace under a nitrogen purge at 800° C. for 4 hours (Table 16).

TABLE 16 Properties of the pyrolyzed extrudate from Example 2 Radial N₂BET BJH N₂ Diameter Piece Surface Pore at cross Crush Area Volumesection Strength (m²/g) (cm³/g) (mm) (N/mm) 169 0.23 1.4 13

Example 17. Preparation of Carbon Black Extrudates, Using BatchPyrolysis in a Rotary Tube Furnace

An aqueous solution (3813 g) containing 4.0 wt % of Dow Cellosize HEC QP40 hydroxyethylcellulose (viscosity 80-125 cP at 2% in H₂O (20° C.)),and 56.0 wt % glucose (ADM Corn Processing, Dextrose Monohydrate 99.7DEwith 91.2 wt % Glucose content) was prepared by stirring 153 ghydroxyethylcellulose and 2340 g Dextrose Monohydrate in 1320 ml D.I.water at approximately 80° C. for 3 hours. This viscous solution wasadded over 3.5 minutes to 1670 g of Sid Richardson SC159 carbon blackpowder in a mix-muller, the mixture was then mixed for a further 20minutes in the mix-muller. The material was then loaded into a 2″diameter Bonnot extruder, fitted with 5 dies with 26 cylindrical holeseach 1/16″ internal diameter (JMP Industries, part number 0388P062), andno spacer, and extruded into spaghetti-like strings. 3.9 kg of theextrudate was dried in a 110° C. oven overnight, to produce 2.93 kg ofdried extrudate. This dried extrudate was then screened over an 18 meshscreen, and 2.91 kg of screened material were collected.

The mixing, extrusion, drying and screening procedure above was repeated3 more times to generate a total of 4 batches of dried, screenedextrudate, which were combined, as summarized in Table 17.

TABLE 17 Production of Carbon Black Extrudate in a 2″ Extruder Mass ofdried Mass of wet Mass extrudate extrudate of dried after Samplecollected extrudate screening number (kg) (kg) (kg) 17.1 3.90 2.93 2.9117.2 4.66 3.80 3.76 17.3 5.17 4.24 4.20 17.4 4.85 3.74 3.71 CombinedTotal 18.58 14.71 14.58

650 g batches of the combined dried & screened extrudate of were thenpyrolyzed in a rotary tube furnace under a nitrogen purge at 800° C. for2 hours, each batch producing approximately 350 g of pyrolyzed product.For each batch, 650 g of the carbon black extrudates (prepared from SidRichardson SC159 with glucose and hydroxyethylcellulose binders) wereloaded into an MTI Corporation 5″ Quartz Tube Three Zone Rotary TubeFurnace (OTF-1200X-5L-R-III-UL). The carbon black extrudates werepyrolyzed with the 5″ quartz tube rotating at 4.0 rpm under a nitrogenatmosphere at 800° C. for 2 hours with the following temperature ramp:ambient temperature to 200° C. at 10° C./min, 200° C. to 600° C. at 5°C./min, 600° C. to 800° C. at 10° C./min, hold at 800° C. for 2 hours,then allowed to cool to ambient temperature, still under nitrogen purge.350 g of pyrolyzed carbon black extrudates were recovered, with 51.5%yield by mass. The properties of the batch-pyrolyzed extrudate are shownin Table 18. Other carbon black extrudates can be pyrolyzed at varioustemperatures in a similar manner, or using a continuously operatingrotary kiln as described in the next example.

TABLE 18 Properties of Carbon Black Extrudate Batch- Pyrolyzed in aRotary Tube Furnace N₂ N₂ Radial BET Mean BJH N₂ Piece Surface Pore PoreCrush Area Diameter Volume Strength (m²/g) (Å) (cm³/g) (N/mm) Combined191 100 0.29 15 Extrudates of Example 17 Batch- Pyrolyzed at 800° C. for2 hours

Example 18. Preparation of Carbon Black Extrudates, Using ContinuousPyrolysis in Rotary Kiln

The mixing, extrusion, drying and screening procedure described inExample 17 was repeated 10 more times to generate an additional 33.4 kgof dried, screened extrudate, which were combined. 25.7 kg of thecombined dried & screened extrudate was then pyrolyzed in a continuousrotary kiln, with a continuous nitrogen purge (counter current flow vs.the extrudate), with a continuous feed of dried extrudate atapproximately 0.5 kg/hour, with product collected at a number of setpoint conditions summarized in Table 19. The rotary kiln waselectrically heated; the temperature set points for the external heatersare shown in Table 19, along with the calculated residence time of thematerial in the heating zone. The temperature and residence time wereadjusted to influence the surface area of the product. A total of 12.5kg of pyrolyzed product was collected, for an overall mass-based yieldof 48.5%.

TABLE 19 Properties of Carbon Black Extrudate Pyrolyzed in aContinuously Operated Rotary Kiln Continuous Rotary TemperatureCalculated Kiln Set Residence N₂ Pyrolyzed Point in Time in SpecificExtrudate Heating Heating Surface Sample Zone Zone Area Number (° C.)(minutes) (m²/g) 18.1 820 63 219 18.2 820 44 208 18.3 800 44 202 18.4780 44 188 18.5 760 44 188 18.6 780 33 176 18.7 820 33 181

Example 19. Hydrodeoxygenation of Glucaric Acid Dilactone to Adipic Acid

Suitably concentrated aqueous solutions of rhodium nitrate and platinumnitrate were added together to carbon black powder (crushed from carbonblack pellets) by incipient wetness impregnation and agitated toimpregnate supports. The samples were dried in an oven at 60° C.overnight, and reduced at 350° C. under a forming gas (5% H₂ and 95% N₂)atmosphere for 4 hours with 2° C./min temperature ramp rate to producecatalysts with a composition of 1.0 wt. % Rh and 2.0 wt. % Pt. By usingother carbon blacks supports, Rh and Pt precursors, and adjusting amountof Rh and Pt in solution, different catalysts with various Rh and Ptloadings on a variety of particles from extrudates were prepared in asimilar manner.

These catalysts were tested for hydrodeoxygenation of glucaric aciddilactone using the following testing protocol. Catalyst (16 mg) wasweighed into a glass vial insert followed by addition of a solution (125μl) containing glucaric acid dilactone (0.80 M), HBr (0.80 M), and water(2.0 M). The glass vial insert was loaded into a reactor and the reactorwas closed. The atmosphere in the reactor was replaced with hydrogen andpressurized to 900 psig at room temperature. Reactor was heated to 120°C. and maintained at 120° C. for 1 hour while vials were shaken. Reactorwas then heated to 160° C. and maintained at 160° C. for 2 hours whilevials were shaken. After that, shaking was stopped and reactor wascooled to 40° C. Pressure in the reactor was slowly released. The glassvial insert was removed from reactor and centrifuged. The clear solutionwas hydrolyzed with NaOH, diluted with deionized water, and analyzed byion chromatography to determine the yield of adipic acid. The propertiesof the carbon black starting materials and results of the reactionscreening are presented in Table 20.

TABLE 20 Adipic Mean Adipic Acid Surface Pore Pore Acid Select- AreaDiameter Volume Yield ivity Support (m²/g) (Å) (cm³/g) (%) (%) CabotMonarch 120 25 277 0.1 75 83 Cabot Monarch 280 30 176 0.1 81 91 TimcalEnsaco 250P 64 140 0.24 92 99 Cabot Monarch 570 102 138 0.3 87 97 CabotMonarch 700 181 121 0.38 89 99 Cabot Vulcan XC72 224 161 0.43 86 99 SidRichardson SC159 234 182 0.81 75 86

Example 20. Testing of Rh/Pt Carbon Black Extrudate Catalysts in aFixed-Bed Reactor for Hydrodeoxygenation of Glucaric Acid to Adipic Acid

Cabot Vulcan XC72 carbon black particles used in this experiment were150 to 300 μm sized particles crushed and sieved from extrudate pelletsprepared from the method described in previous examples. Reactions wereconducted in a 6.4 mm (0.25 inch) OD by 38 cm long zirconium tube withco-current down-flow of gas and liquid. Catalyst beds were vibrationpacked with 200 to 300 μm sized glass beads at the top to approximately5 cm depth, followed by catalyst (28 cm bed depth containing 1.9 g, 0.90wt. % Rh+2.1 wt. % Pt on carbon black particles, 150 to 300 μm particlesize), then 200 to 300 μm sized glass beads at the bottom toapproximately 5 cm depth. Quartz wool plugs separated the catalyst bedfrom the glass beads.

The packed reactor tube was clamped in an aluminum block heater equippedwith PID controller. Gas (compressed hydrogen) and liquid flows wereregulated by mass flow controller and HPLC pump, respectively. Substratesolution contains 0.80M D-glucaric acid-1,4:6,3-dilactone, 0.40M HBr and2.0M water in acetic acid. A back pressure regulator controlled reactorpressure as indicated in Table 21. External temperature of top halfreactor and bottom half reactor was controlled at 110° C. and 160° C.respectively. The catalyst was tested for 350 hours on stream and showedstable performance. Table 21 describes the fixed bed reactor conditionsand resultant catalyst performance.

TABLE 21 Gas Reactor block Glucaric acid Reactor Liquid flowrate/Glucaric acid Adipic temperature/ dilactone pressure/ flowrate/ mL min⁻¹dilactone acid Test ° C. concentration/M psi mL min⁻¹ (STP) conversion/%yield/% 1 110/160 0.80 1000 0.050 50 90 42

Example 21. Hydrodeoxygenation of 1,2,6-Hexanetriol to 1,6-Hexanediol

Suitably concentrated aqueous solutions of Pt(NO₃)_(x) and H₄SiO₄*12WO₃or PtONO₃ and H₄SiO₄*12WO₃ were added to approximately 50 mg of Ensaco250G carbon and agitated to impregnate the supports. The samples weredried in an oven at 40° C. overnight under static air and then reducedat 350° C. under forming gas (5% H₂ and 95% N₂) atmosphere for 3 hours.The final catalysts had a metal content of approximately 4.09 wt. % Ptand 3.42 wt. % W.

These catalysts were tested for 1,2,6-hexanetriol hydrodeoxygenationusing the following catalyst testing protocol. Catalyst (approximately10 mg) was weighed into a glass vial insert followed by addition of anaqueous 1,2,6-hexanetriol solution (200 μl of 0.8 M). The glass vialinsert was loaded into a reactor and the reactor was closed. Theatmosphere in the reactor was replaced with hydrogen and pressurized to670 psig at room temperature. The reactor was heated to 160° C. andmaintained at the respective temperature for 150 minutes while vialswere shaken. After 150 minutes, shaking was stopped and reactor wascooled to 40° C. Pressure in the reactor was then slowly released. Theglass vial insert was removed from the reactor and centrifuged. Thesolution was diluted with methanol and analyzed by gas chromatographywith flame ionization detection. The results are shown in Table 22.

TABLE 22 Surface Mean Pore Pore Area Diameter Volume Pt W YieldSelectivity Support (m²/g) (Å) (cm³/g) Precursor Precursor (%) (%)Ensaco 64 140 0.24 Pt(NO₃)₂ H₄SiO₄*12WO₃ 27 64 250G Ensaco 64 140 0.24PtONO₃ H₄SiO₄*12WO₃ 47 69 250G

Example 22. Hydrodeoxygenation of 1,2,6-Hexanetriol to 1,6-Hexanediol

A suitably concentrated aqueous solution of ammonium metatungstate,H₂₆N₆W₁₂O₄₀ was added to approximately 500 mg of Ensaco 250G andagitated to impregnate the carbon black support. The sample wasthermally treated at 600° C. under a nitrogen atmosphere for 3 hourswith 5° C./min temperature ramp rate. Suitably concentrated aqueoussolutions of Pt(NMe₄)₂(OH)₆ was added to 50 mg of the above sample andagitated to impregnate the carbon supports. The samples were dried in anoven at 40° C. overnight under static air and then reduced at 250° C.under forming gas (5% H₂ and 95% N₂) atmosphere for 3 hours with 5°C./min temperature ramp rate. The final catalysts had a metal content ofapproximately 4.5 wt. % Pt and 2 wt. % W.

These catalysts were tested for 1,2,6-hexanetriol hydrodeoxygenationusing the following catalyst testing protocol. Catalyst (approximately10 mg) was weighed into a glass vial insert followed by addition of anaqueous 1,2,6-hexanetriol solution (200 μl of 0.8 M). The glass vialinsert was loaded into a reactor and the reactor was closed. Theatmosphere in the reactor was replaced with hydrogen and pressurized to670 psig at room temperature. The reactor was heated to 160° C. andmaintained at the respective temperature for 150 minutes while vialswere shaken. After 150 minutes, shaking was stopped and reactor wascooled to 40° C. Pressure in the reactor was then slowly released. Theglass vial insert was removed from the reactor and centrifuged. Theclear solution was diluted with methanol and analyzed by gaschromatography with flame ionization detection. The results are shown inTable 23.

TABLE 23 Surface Mean Pore Pore Area Diameter Volume Pt W YieldSelectivity Support (m²/g) (Å) (cm³/g) Precursor Precursor (%) (%)Ensaco 64 140 0.24 Pt(NMe₄)₂(OH)₆ H₂₆N₆W₁₂O₄₀ 38 88 250G

Example 23. Hydrodeoxygenation of 1,2,6-Hexanetriol to 1,6-Hexanediol

Suitably concentrated aqueous solutions of ammonium metatungstate,H₂₆N₆W₁₂O₄₀ were added to approximately 500 mg of carbon black materialsand agitated to impregnate the carbon black supports. The samples werethermally treated at 600° C. under a nitrogen atmosphere for 3 hourswith 5° C./min temperature ramp rate. Suitably concentrated aqueoussolutions of Pt(NMe₄)₂(OH)₆ were added to approximately 50 mg of theabove samples and agitated to impregnate the carbon supports. Thesamples were dried in an oven at 60° C. under static air and thenreduced at 350° C. under forming gas (5% H₂ and 95% N₂) atmosphere for 3hours with 5° C./min temperature ramp rate. The final catalysts had ametal content of approximately 5.7 wt. % Pt and 1.8 wt. % W.

These catalysts were tested for 1,2,6-hexanetriol hydrodeoxygenationusing the following catalyst testing protocol. Catalyst (approximately10 mg) was weighed into a glass vial insert followed by addition of anaqueous 1,2,6-hexanetriol solution (200 μl of 0.8 M). The glass vialinsert was loaded into a reactor and the reactor was closed. Theatmosphere in the reactor was replaced with hydrogen and pressurized to670 psig at room temperature. The reactor was heated to 160° C. andmaintained at the respective temperature for 150 minutes while vialswere shaken. After 150 minutes, shaking was stopped and reactor wascooled to 40° C. Pressure in the reactor was then slowly released. Theglass vial insert was removed from the reactor and centrifuged. Theclear solution was diluted with methanol and analyzed by gaschromatography with flame ionization detection. Results are shown inTable 24.

TABLE 24 Surface Mean Pore Pore Area Diameter Volume Pt W YieldSelectivity Support (m²/g) (Å) (cm³/g) Precursor Precursor (%) (%)Ensaco 64 140 0.24 Pt(NMe₄)₂(OH)₆ H₂₆N₆W₁₂O₄₀ 52 71 250G Orion 109 1550.32 Pt(NMe₄)₂(OH)₆ H₂₆N₆W₁₂O₄₀ 28 68 HiBlack 40B2

Example 24. Small Scale Batch Reactor Experiments for Amination of1,6-Hexanediol to Produce 1,6-Hexamethylenediamine

Amination of 1,6-Hexanediol to Produce1,6-Hexamethylenediamine—Analytical Details

Product composition was determined by HPLC analysis using a ThermoUltimate 3000 dual analytical chromatography system.Hexamethylenediamine (HMDA), hexamethyleneimine (HMI) and pentylaminewere eluted with a mobile phase consisting of H₂O/MeCN/TFA and detectedusing a charged aerosol detector (CAD). 1,6-Hexanediol (HDO) was elutedwith a mobile phase consisting of H₂O/MeCN/TFA and detected using arefractive index detector (RI). In certain examples an internalstandard, N-methyl-2-pyrrolidone (NMP), was used in the substrate feedto correct for variations in product effluent concentration due to NH₃off-gassing. NMP was eluted with a mobile phase consisting ofH₂O/MeCN/TFA and detected by UV at 210 nm. All products were quantifiedby comparison to calibration standards. Selectivity is reported as theyield of HMDA divided by the sum of HMDA and pentylamine.

Experiment 1

Preparation of Supported Ru Catalysts

A suitably concentrated aqueous solution of Ru(NO)(NO₃)₃ was added to a96 vial array of carbon supports containing 10 or 20 mg of support ineach vial. The volume of ruthenium solution was matched to equal thepore volume of the support. Each sample was agitated to impregnate thesupport. The samples were dried in an oven at 60° C. for 12 hours undera dry air purge. The catalysts were reduced under forming gas (5% H₂ and95% N₂) at 250° C. for 3 hours using a 2° C./min temperature ramp rate.The final catalysts were composed of 2 weight percent ruthenium.

Catalyst Screening Procedure

A substrate solution consisting of 0.7M 1,6-hexanediol in concentratedaqueous NH₄OH was added to an array of catalysts prepared as describedabove. The vials were covered with a Teflon pinhole sheet, a siliconepinhole mat, and a steel gas diffusion plate. The reactor insert wasplaced in a pressure vessel and purged 2× with NH₃ gas. The pressurevessel was charged to 100 psi with NH₃ gas and then to 680 psi with N₂at ambient temperature. The reactor was placed on a shaker and vortexedat 800 rpm at 160° C. After 3 hours, the reactor was cooled to roomtemperature, vented, and purged with nitrogen prior to being unsealed.The samples were diluted with water, mixed, and then centrifuged toseparate catalyst particles. Aliquots were removed from the supernatantand diluted further with dilute aqueous trifluoroacetic acid foranalysis by HPLC. Results are summarized below in Table 25.

TABLE 25 Surface Mean Pore Pore Catalyst HDO HMDA Pentylamine AreaDiameter Volume Amount Conversion Yield Yield Support (m²/g) (Å) (cm³/g)(mg) (%) (%) (%) Selectivity Asbury 80 145 0.28 10 79.8 16.5 0.0 99.85346R Asbury 80 145 0.28 20 99.1 25.1 0.5 97.9 5346R Ensaco 47 136 0.1710 80.8 16.4 0.1 99.5 150G Ensaco 47 136 0.17 20 95.5 24.5 0.7 97.4 150GEnsaco 64 140 0.24 10 78.6 16.3 0.0 100 250G Ensaco 64 140 0.24 20 94.426.0 0.5 98.2 250G Ensaco 63 104 0.18 10 74.7 15.4 0.0 100 260G Ensaco63 104 0.18 20 93.3 24.0 0.5 98.1 260G HP160 158 208 0.87 10 81.7 11.90.0 100 HP160 158 208 0.87 20 98.3 18.3 0.1 99.2 Orion HI- 193 157 0.6610 91.0 18.8 0.2 99.1 Black 50L Orion HI- 193 157 0.66 20 100 21.7 0.796.8 Black 50L Sid 234 182 0.81 10 90.3 14.7 0.0 100 Richardson SC159Sid 234 182 0.81 20 99.3 17.3 0.4 97.9 Richardson SC159 Sid 146 222 0.8710 93.2 19.5 0.1 99.5 Richardson SR155 Sid 146 222 0.87 20 100 19.7 0.498.1 Richardson SR155

Experiment 2

Preparation of Supported Ru/Re Catalysts

Suitably concentrated aqueous solutions of Ru(NO)(NO₃)₃ containingvarying amounts of HReO₄ were added to 0.15 g of a support and agitatedto impregnate the support. The volume of metal solution was matched toequal the pore volume of the support. The samples were dried in an ovenat 60° C. for 3 hours under a dry air purge. Catalyst amounts from 10-20mg were weighed in to glass vials of a 96 vial array. The catalysts werereduced under forming gas (5% H₂ and 95% N₂) at 60° C. for 3 hours thenat 250° C. for 3 hours using a 2° C./min temperature ramp rate. Thefinal catalysts were composed of 4.04 weight percent rutheniumcontaining various rhenium loadings of 0, 0.4, 0.7, and 1.9 wt. %.

Catalyst Screening Procedure

A substrate solution consisting of 1.549M 1,6-hexanediol in concentratedaqueous NH₄OH was added to an array of catalysts prepared as describedabove. The vials were covered with a Teflon pinhole sheet, a siliconepinhole mat, and a steel gas diffusion plate. The reactor insert wasplaced in a pressure vessel and purged 2× with NH₃ gas. The pressurevessel was charged to 100 psi with NH₃ gas and then to 680 psi with N₂at ambient temperature. The reactor was placed on a shaker and vortexedat 800 rpm at 160° C. After 3 hours, the reactor was cooled to roomtemperature, vented, and purged with nitrogen prior to being unsealed.The samples were diluted with water, mixed, and then centrifuged toseparate catalyst particles. Aliquots were removed from the supernatantand diluted further with dilute aqueous trifluoroacetic acid foranalysis by HPLC. Results are outline below in Table 26.

TABLE 26 Hexanediol to Hexamethylenediamine using Ru/Re/Carbon HP-160Catalysts Cata- HDO Pentyl- lyst Conver- HMDA amine HMDA/ En- Amount RuRe sion Yield Yield Pentyl- try (mg) (wt. %) (wt. %) (%) (%) (%) amine 120 4.04 0.0 95.8 20.2 1.4 14.5 2 20 4.04 0.4 98.7 23.2 1.3 18.1 3 204.04 0.7 99.4 23.4 1.0 23.3 4 20 4.04 1.9 97.4 20.3 0.4 51.8 5 10 4.040.0 79.5 14.4 0.6 26.1 6 10 4.04 0.4 90.4 20.1 0.7 27.9 7 10 4.04 0.792.6 20.7 0.6 35.8 8 10 4.04 1.9 78.3 11.5 0.0

Experiment 3

Preparation of Ni/Ru Catalysts Supported on Ensaco 250G

Suitably concentrated aqueous solutions containing Ni(NO₃)₂ and/orRu(NO)(NO₃)₃ were added by incipient wetness impregnation toapproximately 0.4 g of a carbon black support and agitated to impregnatethe support. The volume of metal solution was matched to equal the porevolume of the support. Each catalyst was thermally treated under N₂ in atube furnace at 60° C. for 12 hours then at 300° C. for 3 hours using a5° C./min temperature ramp rate.

Catalyst amounts from 15-25 mg were weighed in to glass vials of a 96vial array. The catalysts were reduced under forming gas (5% H₂ and 95%N₂) at 450° C. for 3 hours using a 2° C./min temperature ramp rate.Catalysts were passivated with 1% O₂ in N₂ at room temperature beforeremoving from the tube furnace.

Catalyst Screening Procedure A

A substrate solution consisting of 0.7M 1,6-hexanediol in concentratedaqueous NH₄OH was added to an array of catalysts prepared as describedabove. The vials were covered with a Teflon pinhole sheet, a siliconepinhole mat, and a steel gas diffusion plate. The reactor insert wasplaced in a pressure vessel and purged 2× with NH₃ gas. The pressurevessel was charged to 100 psi with NH₃ gas and then to 680 psi with N₂at ambient temperature. The reactor was placed on a shaker and vortexedat 800 rpm at 160° C. After 3 hours, the reactor was cooled to roomtemperature, vented, and purged with nitrogen prior to being unsealed.The samples were diluted with water, mixed, and then centrifuged toseparate catalyst particles. Aliquots were removed from the supernatantand diluted further with dilute aqueous trifluoroacetic acid foranalysis by HPLC. Results are summarized below in Table 27.

TABLE 27 Cata- HDO Pentyl- lyst Conver- HMDA amine En- Amount Ni Ru sionYield Yield Selec- try (mg) (wt. %) (wt. %) (%) (%) (%) tivity 1 15 12 035.8 1.9 0.0 98.4 2 15 0 0.56 66.1 9.6 0.3 97.4 3 15 4 0.56 74.3 17.30.3 98.5 4 15 8 0.56 77.3 22.7 0.3 98.7 5 15 12 0.56 85.9 25.3 0.4 98.66 25 12 0 54.0 7.7 0.1 99.1 7 25 0 0.56 82.7 18.9 0.5 97.2 8 25 4 0.5689.1 29.0 0.8 97.5 9 25 8 0.56 92.8 31.4 0.7 97.7 10 25 12 0.56 94.730.1 0.7 97.6

Catalyst Screening Procedure B

Passivated catalysts were reactivated in water under H₂ at 180° C. for 3hours. Most of the water was removed from each catalyst leaving behindenough to act as a protective layer. The catalysts were then screened asdescribed above in Procedure A. Results are summarized below in Table28.

TABLE 28 Cata- HDO Pentyl- lyst Conver- HMDA amine En- Amount Ni Ru sionYield Yield Selec- try (mg) (wt. %) (wt. %) (%) (%) (%) tivity 1 15 12 049.2 7.2 0.00 100.0 2 15 0 0.56 67.0 11.2 0.06 99.5 3 15 4 0.56 73.718.2 0.07 99.7 4 15 8 0.56 86.8 25.5 0.38 98.5 5 15 12 0.56 86.0 23.80.33 98.7 6 25 12 0 73.3 16.0 0.00 100.0 7 25 0 0.56 83.8 18.3 0.84 95.68 25 4 0.56 93.5 28.1 1.22 95.9 9 25 8 0.56 94.0 27.8 1.07 96.3 10 25 120.56 96.1 27.3 1.15 96.0

Fixed Bed Experiments

Preparation of 2 wt. % Ru on Carbon Ensaco 250G

A carbon extrudate, prepared from carbon black Ensaco 250G and acarbohydrate binder, was crushed and sized to 150-300 um. A suitablyconcentrated aqueous solution of Ru(NO)(NO₃)₃ was added to 4.77 g of thecrushed extrudate and agitated to impregnate the support. The volume ofmetal solution was matched to equal the pore volume of the support. Thesamples were dried in an oven at 60° C. for 12 hours under a dry airpurge. The catalyst was reduced under forming gas (5% H₂ and 95% N₂) at250° C. for 3 hours using a 2° C./min temperature ramp rate. Thecatalyst was washed with water and again sized to 106-300 um to removeany fines that may have been generated during the metal impregnationstep.

Preparation of 10.5 wt. % Ni and 0.45 wt. % Ru on Carbon Ensaco 250G

A carbon extrudate, prepared from carbon black Ensaco 250G and acarbohydrate binder, was crushed and sized to 106-300 um. A suitablyconcentrated aqueous solution containing Ni(NO₃)₂.6H₂O and Ru(NO)(NO₃)₃was added to 10 g of the crushed extrudate and agitated to impregnatethe support. The volume of metal solution was matched to equal the porevolume of the support. The catalyst was dried in an oven at 60° C. for12 hours under a dry air purge then thermally treated under N₂ at 300°C. for 3 hours. The catalyst was reduced under forming gas (5% H₂ and95% N₂) at 450° C. for 3 hours using a 2° C./min temperature ramp rate.After cooling to room temperature the catalyst was passivated with 1% O₂in N₂ at room temperature before removing from the tube furnace. Thecatalyst was washed with water and again sized to 106-300 um to removeany fines that may have been generated during the metal impregnationstep.

2 wt. % Ru on Carbon Catalyst

The reaction was performed in a 0.25 inch OD by 570 mm long 316stainless steel tube with a 2 um 316 stainless steel frit at the bottomof the catalyst bed. The reactor was vibration packed with 1 g of SiCbeads (90-120 um) followed by 3 g of a 2% by weight ruthenium on carbonEnsaco 250G catalyst (100-300 um) and finally 2.5 g of SiC beads at thetop. A ¼ inch layer of glass wool was used between each layer. Thepacked reactor tube was vertically mounted in an aluminum block heaterequipped with PID controller. An HPLC pump was used to deliver liquidfeed to the top of the reactor and a back pressure regulator was used tocontrol reactor pressure. The reaction was run at 160° C. Producteffluent was collected periodically for analysis by HPLC. No decline incatalyst activity was observed after 1650 h.

Three different feed compositions were investigated at 160° C. with areactor pressure ranging from 800-1000 psi. In all casesN-methyl-2-pyrrolidone (NMP) was used as an internal standard.

Feed 1: 0.7M 1,6-hexanediol and 0.14M NMP in concentrated NH₄OH.

Feed 2: 0.7M 1,6-hexanediol, 0.14M hexamethyleneimine, and 0.14M NMP inconcentrated NH₄OH.

Feed 3: 1.54M 1,6-hexanediol, 0.308M hexamethyleneimine, and 0.308M NMPin concentrated NH₄OH.

The results are summarized below in Table 29.

10.5 wt. % Ni/0.45 wt. % Ru on Carbon Catalyst

The reaction was performed as described above for the Ru only catalyst.A total of 3 g of Ni/Ru catalyst was loaded into the reactor andreactivated at 180° C. under H₂ before introduction of the feedsolution. No decline in catalyst activity was observed after 650 h.Results are summarized below in Table 29.

TABLE 29 Feed Reactor HDO HMDA HMI Pentylamine Rate Pressure ConversionYield Yield Yield Catalyst Source (mL/min) (psi) (%) (%) (%) (%)Selectivity 2 wt. % Ru Feed 1 0.2 800 85 23 11 1.5 93.9 2 wt. % Ru Feed2 0.2 800 83 29 18 1.6 94.8 2 wt. % Ru Feed 3 0.15 1000 90 36 21 2.693.3 10.5 wt. % Feed 2 0.2 800 83 26 17 0.5 98.1 Ni/0.45%Ru

When introducing elements of the present invention or the preferredembodiments(s) thereof, the articles “a”, “an”, “the” and “said” areintended to mean that there are one or more of the elements. The terms“comprising”, “including” and “having” are intended to be inclusive andmean that there may be additional elements other than the listedelements.

In view of the above, it will be seen that the several objects of theinvention are achieved and other advantageous results attained.

As various changes could be made in the above compositions, methods, andprocesses without departing from the scope of the invention, it isintended that all matter contained in the above description and shown inthe accompanying drawing[s] shall be interpreted as illustrative and notin a limiting sense.

Having described the invention in detail, it will be apparent thatmodifications and variations are possible without departing from thescope of the invention defined in the appended claims.

1-146. (canceled)
 147. A process for the selective oxidation of analdose to an aldaric acid comprising reacting the aldose with oxygen inthe presence of a catalyst composition to form the aldaric acid, whereinthe catalyst composition comprises a shaped porous carbon product as acatalyst support and a catalytically active component, wherein theshaped porous carbon product comprises: (a) carbon black and (b) acarbonized binder comprising a carbonization product of a water solubleorganic binder and wherein the shaped porous carbon product has a BETspecific surface area from about 20 m²/g to about 500 m²/g, a mean porediameter greater than about 5 nm, a specific pore volume greater thanabout 0.1 cm³/g, a carbon black content of at least about 35 wt. %, anda carbonized binder content from about 20 wt. % to about 50 wt. %.148-160. (canceled)
 161. The process of claim 147, wherein the aldosecomprises a pentose and/or a hexose.
 162. The process of claim 161,wherein the pentose comprises ribose, arabinose, xylose, and/or lyxose.163. The process of claim 161, wherein the hexose comprises glucose,allose, altrose, mannose, gulose, idose, galactose, and/or talose. 164.The process of claim 147, wherein the aldaric acid is selected from thegroup consisting of xylaric acid and glucaric acid.
 165. The process ofclaim 147, wherein the aldaric acid comprises glucaric acid.
 166. Theprocess of claim 147, wherein the catalytically active component of thecatalyst composition comprises platinum.
 167. The process of claim 147,wherein, wherein the catalytically active component of the catalystcomposition comprises platinum and gold.
 168. The process of claim 147,wherein the aldaric acid comprises glucaric acid and the glucaric acidyield is at least about 30%.
 169. The process of claim 147, wherein thealdose comprises glucose and the catalytically active componentcomprises platinum and the mass ratio of glucose to platinum is fromabout 10:1 to about 1000:1.
 170. The process of claim 147, wherein theshaped porous carbon product has a BET specific surface area from about20 m²/g to about 350 m²/g.
 171. The process of claim 147, wherein theshaped porous carbon product has a mean pore diameter from about 5 nm toabout 100 nm.
 172. The process of claim 147, wherein the bindercomprises a saccharide selected from the group consisting of amonosaccharide, a disaccharide, an oligosaccharide, and combinationsthereof.
 173. The process of claim 147, wherein the binder comprises amonosaccharide selected from the group consisting of glucose, fructose,hydrate thereof, syrup thereof, and combinations thereof.
 174. Theprocess of claim 147, wherein the binder comprises a polymericcarbohydrate, derivative of a polymeric carbohydrate, or anon-carbohydrate synthetic polymer, or any combination thereof.
 175. Theprocess of claim 174, wherein the polymeric carbohydrate or derivativeof the polymeric carbohydrate comprises a cellulosic compound selectedfrom the group consisting of methylcellulose, ethylcellulose,ethylmethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose,methylhydroxyethylcellulose, ethylhydroxyethylcellulose,hydroxypropylmethylcellulose, carboxymethylcellulose, and mixturesthereof.
 176. The process of claim 174, wherein the polymericcarbohydrate or derivative of the polymeric carbohydrate comprises astarch.
 177. The process of claim 174, wherein the non-carbohydratesynthetic polymer is selected from the group consisting of polyacrylicacid, polyvinyl alcohols, polyvinylpyrrolidones, polyvinyl acetates,polyacrylates, polyethers, and copolymers derived therefrom.
 178. Theprocess of claim 147, wherein the binder comprises a saccharide selectedfrom the group consisting of glucose, fructose, hydrates thereof andcombinations thereof and a polymeric carbohydrate or derivative of thepolymeric carbohydrate selected from the group consisting ofhydroxyethylcellulose, methylcellulose, starch and combinations thereof.179. The process of claim 147, wherein the shaped porous carbon producthas a radial piece crush strength greater than about 4.4 N/mm (1 lb/mm)and/or a mechanical piece crush strength greater than about 22 N (5lbs).